U.S. patent application number 15/184693 was filed with the patent office on 2016-10-06 for organometallic compound and organic light-emitting device including the same.
The applicant listed for this patent is SAMSUNG DISPLAY CO., LTD.. Invention is credited to Jong-Won CHOI, Wha-II CHOI, So-Yeon KIM, Yoon-Hyun KWAK, Ji-Youn LEE, Sun-Young LEE, Bum-Woo PARK.
Application Number | 20160293868 15/184693 |
Document ID | / |
Family ID | 49111055 |
Filed Date | 2016-10-06 |
United States Patent
Application |
20160293868 |
Kind Code |
A1 |
CHOI; Jong-Won ; et
al. |
October 6, 2016 |
ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING
THE SAME
Abstract
An organometallic compound may be represented by one selected
from the group of Formulae 5 to 8: ##STR00001##
Inventors: |
CHOI; Jong-Won; (Yongin-si,
KR) ; KWAK; Yoon-Hyun; (Yongin-si, KR) ; PARK;
Bum-Woo; (Yongin-si, KR) ; LEE; Sun-Young;
(Yongin-si, KR) ; CHOI; Wha-II; (Yongin-si,
KR) ; KIM; So-Yeon; (Yongin-si, KR) ; LEE;
Ji-Youn; (Yongin-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SAMSUNG DISPLAY CO., LTD. |
Yongin-si |
|
KR |
|
|
Family ID: |
49111055 |
Appl. No.: |
15/184693 |
Filed: |
June 16, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13803650 |
Mar 14, 2013 |
9373798 |
|
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15184693 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/5056 20130101;
H01L 51/0087 20130101; H01L 51/0081 20130101; H01L 51/0088
20130101; C07F 15/004 20130101; C07F 15/0026 20130101; H01L 51/5092
20130101; C09K 2211/1007 20130101; H01L 51/5016 20130101; C07F
15/0093 20130101; C07F 15/0086 20130101; C07F 15/0033 20130101;
C09K 2211/185 20130101; C09K 2211/1044 20130101; H01L 51/5088
20130101; C09K 11/06 20130101; H01L 51/0085 20130101; C09K
2211/1022 20130101; H01L 51/5096 20130101; H01L 51/5072
20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C09K 11/06 20060101 C09K011/06; C07F 15/00 20060101
C07F015/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 7, 2012 |
KR |
10-2012-0099543 |
Claims
1. An organometallic compound represented by one selected from the
group of Formulae 5 to 8: ##STR00152## wherein, in Formulae 5 to 8:
M is a transition metal; X.sub.1 is N or C(R.sub.5); R.sub.1 to
R.sub.5 are each independently selected from the group of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a substituted or unsubstituted C.sub.1-C.sub.60 alkyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkenyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkynyl
group, a substituted or unsubstituted C.sub.1-C.sub.60 alkoxy
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkenyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryloxy group, a substituted or
unsubstituted C.sub.6-C.sub.60 arylthio group, a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5),
--C(.dbd.O)(Q.sub.6), and a binding site with an adjacent ligand
via a single bond or a divalent linking group; two substituents of
R.sub.1 to R.sub.5 are optionally linked together to form one
selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 hetero alicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; Q.sub.1 to
Q.sub.6 are each independently selected from the group of a
hydrogen atom, a substituted or unsubstituted C.sub.1-C.sub.60
alkyl group, a substituted or unsubstituted C.sub.6-C.sub.60 aryl
group, and a substituted or unsubstituted C.sub.2-C.sub.60
heteroaryl group; m2 is 0, 1, or 2, wherein when m2 is 1 or 2, L is
a monodentate, bidentate, tridentate, or tetradentate organic
ligand; X.sub.12 and X.sub.16d are each independently N or C;
X.sub.21 is N or C(R.sub.51), X.sub.22 is N or C(R.sub.52),
X.sub.23 is N or C(R.sub.53), X.sub.24 is N or C(R.sub.54),
X.sub.25 is N or C(R.sub.55), X.sub.26 is N or C(R.sub.56),
X.sub.27 is N or C(R.sub.57), X.sub.28 is N or C(R.sub.58), and
X.sub.29 is N or C(R.sub.59); R.sub.41, R.sub.42, and R.sub.51 to
R.sub.59 are each independently selected from the group of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a substituted or unsubstituted C.sub.1-C.sub.60 alkyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkenyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkynyl
group, a substituted or unsubstituted C.sub.1-C.sub.60 alkoxy
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkenyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryloxy group, a substituted or
unsubstituted C.sub.6-C.sub.60 arylthio group, a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.11)(Q.sub.12), --Si(Q.sub.13)(Q.sub.14)(Q.sub.15), and a
binding site with an adjacent ligand via a single bond or a
divalent linking group; two adjacent substituents of R.sub.41,
R.sub.42, and R.sub.51 to R.sub.59 are optionally linked together
to form one selected from the group of a substituted or
unsubstituted C.sub.4-C.sub.20 alicyclic ring, a substituted or
unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring, a substituted
or unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted
or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; and Q.sub.11
to Q.sub.15 are each independently selected from the group of a
hydrogen atom, a C.sub.1-C.sub.10 alkyl group, a C.sub.6-C.sub.20
aryl group, and a C.sub.2-C.sub.20 heteroaryl group.
2. The organometallic compound as claimed in claim 1, wherein: the
organometallic compound is represented by one selected from the
group of Formulae 5-(1), 5-(2), 5-(3), and 5-(4): ##STR00153##
wherein, in Formulae 5-(1) to 5-(4): M, X.sub.1, and R.sub.1 to
R.sub.5 are as defined in Formulae 5 to 8; m2 is 0, 1, or 2,
wherein when m2 is 1 or 2, L is as defined in Formulae 5 to 8;
X.sub.21 is N or C(R.sub.51), X.sub.22 is N or C(R.sub.52),
X.sub.23 is N or C(R.sub.53), X.sub.24 is N or C(R.sub.54),
X.sub.25 is N or C(R.sub.55), and X.sub.26 is N or C(R.sub.56); and
R.sub.41, R.sub.51 to R.sub.56, R.sub.61 to R.sub.68, and R.sub.71
to R.sub.74 are each independently selected from the group of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20
alkoxy group, a substituted C.sub.1-C.sub.20 alkyl group, a
substituted C.sub.1-C.sub.20 alkoxy group, a phenyl group, a
naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, a triazinyl group,
and a substituted cyclic group that is substituted with at least
one selected from the group of: a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; the substituted C.sub.1-C.sub.20 alkyl group
and the substituted C.sub.1-C.sub.20 alkoxy group are each
substituted with at least one selected from the group of a
deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a
nitro group, and an amino group; and the substituted cyclic group
is selected from the group of a substituted phenyl group, a
substituted naphthyl group, a substituted anthryl group, a
substituted fluorenyl group, a substituted carbazolyl group, a
substituted pyridinyl group, a substituted pyrimidinyl group, and a
substituted triazinyl group.
3. The organometallic compound as claimed in claim 1, wherein: the
organometallic compound is represented by one selected from the
group of Formulae 5-(a), 6-(a), and 7-(a): ##STR00154## wherein, in
Formulae 5-(a), 6-(a), and 7-(a): M, X.sub.1, and R.sub.2 to
R.sub.5 are as defined in Formulae 5 to 8; m2 is 0, 1, or 2,
wherein, when m2 is 1 or 2, L is as defined in Formulae 5 to 8;
X.sub.12 is C or N; X.sub.21 is N or C(R.sub.51), X.sub.22 is N or
C(R.sub.52), X.sub.23 is N or C(R.sub.53), X.sub.24 is N or
C(R.sub.54), X.sub.25 is N or C(R.sub.55), X.sub.26 is N or
C(R.sub.56), and X.sub.27 is N or C(R.sub.57); R.sub.41 and
R.sub.51 to R.sub.57 are each independently selected from the group
of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl
group, a cyano group, a nitro group, an amino group, an amidino
group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a C.sub.1-C.sub.20 alkyl group, a
C.sub.1-C.sub.20 alkyl group substituted with at least one fluorine
atom, a C.sub.1-C.sub.20 alkoxy group, a phenyl group, a naphthyl
group, and an anthryl group; Y.sub.2 is a single bond or a divalent
linking group including at least one selected from the group of
--O--, --S--, --N(Z.sub.11)--, --[C(Z.sub.12)(Z.sub.13)].sub.c--,
and --[Si(Z.sub.14)(Z.sub.15)].sub.d--; Z.sub.11 to Z.sub.15 are
each independently selected from the group of a hydrogen atom, a
deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a
nitro group, an amino group, an amidino group, a hydrazine, a
hydrazone, a carboxyl group or a salt thereof, a sulfonic acid
group or a salt thereof, a phosphoric acid group or a salt thereof,
C.sub.1-C.sub.60 alkyl group, a C.sub.1-C.sub.60 alkyl group
substituted with at least one halogen atom, a C.sub.2-C.sub.60
alkenyl group, a C.sub.2-C.sub.60 alkynyl group, a C.sub.1-C.sub.60
alkoxy group, a C.sub.3-C.sub.10 cycloalkyl group, a
C.sub.3-C.sub.10 cycloalkenyl group, a C.sub.3-C.sub.10
heterocycloalkyl group, a C.sub.3-C.sub.10 heterocycloalkenyl
group, a C.sub.6-C.sub.60 aryl group, or a C.sub.2-C.sub.60
heteroaryl group; and c and d are each independently an integer
from 1 to 4.
4. An organic light-emitting device, comprising: a substrate; a
first electrode; a second electrode opposite the first electrode;
and an organic layer between the first electrode and the second
electrode, the organic layer including the organometallic compound
as claimed in claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional application based on pending
application Ser. No. 13/803,650, filed Mar. 14, 2013, the entire
contents of which is hereby incorporated by reference.
[0002] The present application claims priority under 35 U.S.C.
.sctn.119 to Korean Patent Application No. 10-2012-0099543, filed
on Sep. 7, 2012, in the Korean Intellectual Property Office, and
entitled: "Organometallic Compound and Organic Light Emitting
Device Including the Same," which hereby incorporated by reference
in its entirety.
BACKGROUND OF THE INVENTION
[0003] 1. Field
[0004] Embodiments relate to a compound for organic light-emitting
devices, and an organic light-emitting device including the
compound.
[0005] 2. Description of the Related Art
[0006] Organic light-emitting devices (OLEDs) may be light emitting
devices (e.g., self-emitting devices) and may have advantages such
as wide viewing angles, excellent contrast, quick response, high
brightness, excellent driving voltage characteristics, and the
ability to provide multicolored images.
SUMMARY
[0007] Embodiments are directed to an organometallic compound
represented by Formula 1:
##STR00002##
[0008] wherein, in Formula 1: M may be a transition metal; X.sub.1
may be N or C(R.sub.5); R.sub.1 to R.sub.5 each independently may
be selected from the group of a hydrogen atom, a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a substituted or
unsubstituted C.sub.1-C.sub.60 alkyl group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkenyl group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkynyl group, a substituted or
unsubstituted C.sub.1-C.sub.60 alkoxy group, a substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkenyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 heterocycloalkyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 heterocycloalkenyl
group, a substituted or unsubstituted C.sub.6-C.sub.60 aryl group,
a substituted or unsubstituted C.sub.6-C.sub.60 aryloxy group, a
substituted or unsubstituted C.sub.6-C.sub.60 arylthio group, a
substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5),
--C(.dbd.O)(Q.sub.6), and a binding site with an adjacent ligand
via a single bond or a divalent linking group; two substituents of
R.sub.1 to R.sub.5 may be optionally linked together to form one
selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 hetero alicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; Q.sub.1 to
Q.sub.6 each independently may be selected from the group of a
hydrogen atom, a substituted or unsubstituted C.sub.1-C.sub.60
alkyl group, a substituted or unsubstituted C.sub.6-C.sub.60 aryl
group, and a substituted or unsubstituted C.sub.2-C.sub.60
heteroaryl group; n may be an integer from 1 to 3; L may be a
monodentate, bidentate, tridentate, or tetradentate organic ligand;
and m may be an integer from 0 to 4.
[0009] M may be selected from the group of ruthenium (Ru), rhodium
(Rh), palladium (Pd), tungsten (W), rhenium (Re), osmium (Os),
iridium (Ir), and platinum (Pt).
[0010] X.sub.1 may be C(R.sub.5).
[0011] X.sub.1 may be N.
[0012] X.sub.1 may be C(R.sub.5); R.sub.1 to R.sub.5 each
independently may be one selected from the group of a hydrogen
atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano
group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a methyl group, an ethyl group, an n-propyl group, an
i-propyl group, an n-butyl group, an i-butyl group, a t-butyl
group, a pentyl group, a hexyl group, a heptyl group, an octyl
group, a nonyl group, a decyl group, a methoxy group, an ethoxy
group, a propoxy group, a butoxy group, a pentoxy group, and a
substituted group that is substituted with at least one selected
from the group of a deuterium atom, a fluorine atom, a hydroxyl
group, a cyano group, a nitro group, and an amino group; and the
substituted group may be selected from the group of a substituted
methyl group, a substituted ethyl group, a substituted n-propyl
group, a substituted i-propyl group, a substituted n-butyl group, a
substituted i-butyl group, a substituted t-butyl group, a
substituted pentyl group, a substituted hexyl group, a substituted
heptyl group, a substituted octyl group, a substituted nonyl group,
a substituted decyl group, a substituted methoxy group, a
substituted ethoxy group, a substituted propoxy group, a
substituted butoxy group, and a substituted pentoxy group.
[0013] X.sub.1 may be N; R.sub.1 to R.sub.4 each independently may
be one selected from the group of a hydrogen atom, a deuterium
atom, a halogen atom, a hydroxyl group, a cyano group, a nitro
group, an amino group, an amidino group, a hydrazine, a hydrazone,
a carboxyl group or a salt thereof, a sulfonic acid group or a salt
thereof, a phosphoric acid group or a salt thereof, a methyl group,
an ethyl group, an n-propyl group, an i-propyl group, an n-butyl
group, an i-butyl group, a t-butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, a decyl
group, a methoxy group, an ethoxy group, a propoxy group, a butoxy
group, and pentoxy group, and a substituted group that is
substituted with at least one selected from the group of a
deuterium atom, a fluorine atom, a hydroxyl group, a cyano group, a
nitro group, and an amino group; and the substituted group may be
selected from the group of a substituted methyl group, a
substituted ethyl group, a substituted n-propyl group, a
substituted i-propyl group, a substituted n-butyl group, a
substituted i-butyl group, a substituted t-butyl group, a
substituted pentyl group, a substituted hexyl group, a substituted
heptyl group, a substituted octyl group, a substituted nonyl group,
a substituted decyl group, a substituted methoxy group, a
substituted ethoxy group, a substituted propoxy group, a
substituted butoxy group, and a substituted pentoxy group.
[0014] i) R.sub.2 and R.sub.3 may be linked together so that the
organometallic compound is represented by Formula 1A; ii) X.sub.1
may be C(R.sub.5), and R.sub.4 and R.sub.5 may be linked together
so that the organometallic compound is represented by Formula 1B;
or iii) R.sub.2 and R.sub.3 may be linked together, X.sub.1 may be
C(R.sub.5), and R.sub.4 and R.sub.5 may be linked together so that
the organometallic compound is represented by Formula 1C:
##STR00003##
[0015] wherein, in Formulae 1A, 1B, and 1C: M, X.sub.1, R.sub.1 to
R.sub.5, n, L, and m may be as in Formula 1; and the A ring and the
B ring each independently may be selected from the group of a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
a substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, and
a substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic
ring.
[0016] The organometallic compound may be represented by Formula 1A
or Formula 1C; the A ring may be at least one selected from the
group of benzene, pentalene, indene, naphthalene, azulene,
heptalene, indacene, acenaphthylene, fluorene, spiro-fluorene,
phenalene, phenanthrene, anthracene, fluoranthene, triphenylene,
pyrene, chrysene, and a substituted group that is substituted with
at least one selected from the group of: a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.60 alkyl
group, a C.sub.1-C.sub.60 alkyl group substituted with at least one
halogen atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60
alkynyl group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, a
C.sub.6-C.sub.60 aryloxy group, a C.sub.6-C.sub.60 arylthio group,
a C.sub.2-C.sub.60 heteroaryl group, --N(Q.sub.11)(Q.sub.12), and
--Si(Q.sub.13)(Q.sub.14)(Q.sub.15); Q.sub.11 to Q.sub.15 each
independently may be selected from the group of a hydrogen atom, a
C.sub.1-C.sub.10 alkyl group, a C.sub.6-C.sub.20 aryl group, and a
C.sub.2-C.sub.20 heteroaryl group; and the substituted group may be
selected from the group of a substituted benzene, a substituted
pentalene, a substituted indene, a substituted naphthalene, a
substituted azulene, a substituted heptalene, a substituted
indacene, a substituted acenaphthylene, a substituted fluorene, a
substituted spiro-fluorene, a substituted phenalene, a substituted
phenanthrene, a substituted anthracene, a substituted fluoranthene,
a substituted triphenylene, a substituted pyrene, and a substituted
chrysene.
[0017] The organometallic compound may be represented by Formula 1B
or Formula 1C; the B ring may be at least one selected from the
group of cyclopropane, cyclobutane, cyclopentane, cyclohexane,
cycloheptane, cyclooctane, cyclopentene, cyclopentadiene,
cyclohexadiene, cycloheptadiene, bicyclo-heptane, bicyclo-octane,
benzene, pentalene, indene, naphthalene, azulene, heptalene,
indacene, acenaphthylene, fluorene, spiro-fluorene, phenalene,
phenanthrene, anthracene, fluoranthene, triphenylene, pyrene,
chrysene, and a substituted group that is substituted with at least
one selected from the group of: a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a C.sub.1-C.sub.60 alkyl group, a
C.sub.1-C.sub.60 alkyl group substituted with at least one halogen
atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60 alkynyl
group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, a
C.sub.6-C.sub.60 aryloxy group, a C.sub.6-C.sub.60 arylthio group,
a C.sub.2-C.sub.60 heteroaryl group, --N(Q.sub.11)(Q.sub.12), and
--Si(Q.sub.13)(Q.sub.14)(Q.sub.15); Q.sub.11 to Q.sub.15 each
independently may be selected from the group of a hydrogen atom, a
C.sub.1-C.sub.10 alkyl group, a C.sub.6-C.sub.20 aryl group, and a
C.sub.2-C.sub.20 heteroaryl group; the substituted group may be
selected from the group of a substituted cyclopropane, a
substituted cyclobutane, a substituted cyclopentane, a substituted
cyclohexane, a substituted cycloheptane, a substituted cyclooctane,
a substituted cyclopentene, a substituted cyclopentadiene, a
substituted cyclohexadiene, a substituted cycloheptadiene, a
substituted bicyclo-heptane, a substituted bicyclo-octane, a
substituted benzene, a substituted pentalene, a substituted indene,
a substituted naphthalene, a substituted azulene, a substituted
heptalene, a substituted indacene, a substituted acenaphthylene, a
substituted fluorene, a substituted spiro-fluorene, a substituted
phenalene, a substituted phenanthrene, a substituted anthracene, a
substituted fluoranthene, a substituted triphenylene, a substituted
pyrene, and a substituted chrysene.
[0018] The organometallic compound may be represented by one
selected from the group of Formulae 1A-(1), 1B-(1), 1B-(2), 1B-(3),
1C-(1), 1C-(2), 1C-(3), and 1D-(1):
##STR00004## ##STR00005##
[0019] wherein, in Formulae 1A-(1), 1B-(1), 1B-(2), 1B-(3), 1C-(1),
1C-(2), 1C-(3), and 1D-(1): R.sub.1 to R.sub.5, R.sub.11 to
R.sub.14, and R.sub.21 to R.sub.28 each independently may be
selected from the group of a hydrogen atom, a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.20 alkyl
group, a C.sub.1-C.sub.20 alkoxy group, a substituted
C.sub.1-C.sub.20 alkyl group, a substituted C.sub.1-C.sub.20 alkoxy
group, a phenyl group, a naphthyl group, an anthryl group, a
fluorenyl group, a carbazolyl group, a pyridinyl group, a
pyrimidinyl group, a triazinyl group, and a substituted cyclic
group that is substituted with at least one selected from the group
of: a deuterium atom, a halogen atom, a hydroxyl group, a cyano
group, a nitro group, an amino group, a C.sub.1-C.sub.20 alkyl
group, a C.sub.1-C.sub.20 alkoxy group, a phenyl group, a naphthyl
group, an anthryl group, a fluorenyl group, a carbazolyl group, a
pyridinyl group, a pyrimidinyl group, and a triazinyl group; the
substituted C.sub.1-C.sub.10 alkyl group and the substituted
C.sub.1-C.sub.20 alkoxy group each may be substituted with at least
one selected from the group of a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, and an amino group;
the substituted cyclic group may be selected from the group of a
substituted phenyl group, a substituted naphthyl group, a
substituted anthryl group, a substituted fluorenyl group, a
substituted carbazolyl group, a substituted pyridinyl group, a
substituted pyrimidinyl group, and a substituted triazinyl group; n
may be an integer from 1 to 3; L may be an organic ligand; and m
may be an integer from 0 to 4.
[0020] m may be 1, 2, 3, or 4; at least one of L.sub.m may be
represented by one selected from the group of Formulae 2A to
2F:
##STR00006##
[0021] wherein, in Formulae 2A to 2F: M.sub.1 may be P or As;
X.sub.11a, X.sub.11b, X.sub.12, X.sub.13, X.sub.14, X.sub.15,
X.sub.16a, X.sub.16b, X.sub.16c, X.sub.16d, X.sub.16e, X.sub.16f,
X.sub.16g, X.sub.17a, X.sub.17b, X.sub.17c, and X.sub.17d each
independently may be selected from the group of C(R.sub.40).sub.x,
N, O, N(R.sub.35), P(R.sub.36)(R.sub.37), and
As(R.sub.38)(R.sub.39); R.sub.33'' and R.sub.34'' each
independently may be selected from the group of a single bond, a
substituted or unsubstituted C.sub.1-C.sub.5 alkylene group, and a
substituted or unsubstituted C.sub.2-C.sub.5 alkenylene group;
R.sub.31, R.sub.32a, R.sub.32b, R.sub.32c, R.sub.33a, R.sub.33b,
R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39, and
R.sub.40 each independently may be selected from the group of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a substituted or unsubstituted C.sub.1-C.sub.60 alkyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkenyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkynyl
group, a substituted or unsubstituted C.sub.1-C.sub.60 alkoxy
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkenyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, and a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group; the C ring, the D
ring, the E ring, the F ring, the G ring, and the H ring each
independently may be selected from the group of a 5-membered to
20-membered saturated ring, and a 5-membered to 20-membered
unsaturated ring; x may be an integer from 0 to 2; and * may be a
binding site with M in Formula 1.
[0022] R.sub.31, R.sub.32a, R.sub.32b, R.sub.32c, R.sub.33a,
R.sub.33b, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, and
R.sub.39 each independently may be selected from the group of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20
alkoxy group, a substituted C.sub.1-C.sub.20 alkyl group, a
substituted C.sub.1-C.sub.20 alkoxy group, a phenyl group, a
naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, and a triazinyl
group, and a substituted cyclic group that is substituted with at
least one selected from the group of: a deuterium atom, a halogen
atom, a hydroxyl group, a cyano group, a nitro group, an amino
group, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy
group, a phenyl group, a naphthyl group, an anthryl group, a
fluorenyl group, a carbazolyl group, a pyridinyl group, a
pyrimidinyl group, and a triazinyl group; the substituted
C.sub.1-C.sub.20 alkyl group and the substituted C.sub.1-C.sub.20
alkoxy group each may be substituted with at least one selected
from the group of a deuterium atom, a halogen atom, a hydroxyl
group, a cyano group, a nitro group, and an amino group; and the
substituted cyclic group may be selected from the group of a
substituted phenyl group, a substituted naphthyl group, a
substituted anthryl group, a substituted fluorenyl group, a
substituted carbazolyl group, a substituted pyridinyl group, a
substituted pyrimidinyl group, and a substituted triazinyl.
[0023] The at least one of L.sub.m may be represented by Formula
2C; and X.sub.11a and X.sub.11b in Formula 2C each independently
may be selected from the group of 0, P(R.sub.36)(R.sub.37), and
As(R.sub.38)(R.sub.39).
[0024] The at least one of L.sub.m may be represented by one
selected from the group of Formulae 2D, 2E, and 2F; the C ring, the
D ring, the E ring, the F ring, the G ring, and the H ring in
Formulae 2D, 2E, and 2F each independently may be a substituted or
unsubstituted benzene, a substituted or unsubstituted pentalene, a
substituted or unsubstituted indene, a substituted or unsubstituted
naphthalene, a substituted or unsubstituted azulene, a substituted
or unsubstituted heptalene, a substituted or unsubstituted
indacene, a substituted or unsubstituted acenaphthylene, a
substituted or unsubstituted fluorene, a substituted or
unsubstituted spiro-fluorene, a substituted or unsubstituted
phenalene, a substituted or unsubstituted phenanthrene, a
substituted or unsubstituted anthracene, a substituted or
unsubstituted fluoranthene, a substituted or unsubstituted
triphenylene, a substituted or unsubstituted pyrene, a substituted
or unsubstituted chrysene, a substituted or unsubstituted pyrrole,
a substituted or unsubstituted imidazole, a substituted or
unsubstituted pyrazole, a substituted or unsubstituted isothiazole,
a substituted or unsubstituted isoxazole, a substituted or
unsubstituted pyridine, a substituted or unsubstituted pyrazine, a
substituted or unsubstituted pyrimidine, a substituted or
unsubstituted pyridazine, a substituted or unsubstituted isoindole,
a substituted or unsubstituted indole, a substituted or
unsubstituted indazole, a substituted or unsubstituted purine, a
substituted or unsubstituted isoquinoline, a substituted or
unsubstituted quinoline, a substituted or unsubstituted
phthalazine, a substituted or unsubstituted quinoxaline, a
substituted or unsubstituted quinazoline, or a substituted or
unsubstituted cinnoline; when the C ring is substituted with at
least two substituents, adjacent two of the at least two
substituents may be optionally linked together to form one selected
from the group of a substituted or unsubstituted C.sub.4-C.sub.20
alicyclic ring, a substituted or unsubstituted C.sub.2-C.sub.20
heteroalicyclic ring, a substituted or unsubstituted
C.sub.6-C.sub.20 aromatic ring, and a substituted or unsubstituted
C.sub.2-C.sub.20 heteroaromatic ring; when the D ring is
substituted with at least two substituents, adjacent two of the at
least two substituents may be optionally linked together to form
one selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; when the E ring
is substituted with at least two substituents, adjacent two of the
at least two substituents may be optionally linked together to form
one selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; when the F ring
is substituted with at least two substituents, adjacent two of the
at least two substituents may be optionally linked together to form
one selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; when the G ring
is substituted with at least two substituents, adjacent two of the
at least two substituents may be optionally linked together to form
one selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; and when the H
ring is substituted with at least two substituents, adjacent two of
the at least two substituents may be optionally linked together to
form one selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring.
[0025] The organometallic compound may be represented by one
selected from the group of Formulae 3 and 4:
##STR00007##
[0026] wherein, in Formulae 3 and 4: M may be a transition metal;
X.sub.1a may be N or C(R.sub.5a); X.sub.1b may be N or C(R.sub.5b);
R.sub.1a to R.sub.5a and R.sub.1b to R.sub.5b each independently
may be a hydrogen atom, a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a substituted or unsubstituted
C.sub.1-C.sub.60 alkyl group, a substituted or unsubstituted
C.sub.2-C.sub.60 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.60 alkynyl group, a substituted or unsubstituted
C.sub.1-C.sub.60 alkoxy group, a substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkenyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 heterocycloalkenyl group, a
substituted or unsubstituted C.sub.6-C.sub.60 aryl group, a
substituted or unsubstituted C.sub.6-C.sub.60 aryloxy group, a
substituted or unsubstituted C.sub.6-C.sub.60 arylthio group, a
substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5),
--C(.dbd.O)(Q.sub.6), and a binding site with an adjacent ligand
via a single bond or a divalent linking group; two substituents of
R.sub.1a to R.sub.5a may be optionally linked together to form one
selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 hetero alicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; two
substituents of R.sub.1b to R.sub.5b may be optionally linked
together to form one selected from the group of a substituted or
unsubstituted C.sub.4-C.sub.20 alicyclic ring, a substituted or
unsubstituted C.sub.2-C.sub.20 hetero alicyclic ring, a substituted
or unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted
or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; Q.sub.1 to
Q.sub.6 each independently may be a hydrogen atom, a substituted or
unsubstituted C.sub.1-C.sub.60 alkyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, and a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group; L may be an
organic ligand; and m may be 0, 1, or 2.
[0027] The organometallic compound may be represented by Formula 3,
and R.sub.1a=R.sub.1b, R.sub.2a=R.sub.2b, R.sub.3a=R.sub.3b,
R.sub.4a=R.sub.4b, X.sub.1a=X.sub.1b), M=Pt, and m1=0.
[0028] The organometallic compound may be represented by Formula 4;
and R.sub.1a=R.sub.1b, R.sub.2a=R.sub.2b, R.sub.3a=R.sub.3b,
R.sub.4a=R.sub.4b, X.sub.1a=X.sub.1b, M=Pt, and m1=0.
[0029] The organometallic compound may be represented by one
selected from the group of Formulae 3A-(1), 3A-(2), 3A-(3), 3A-(4),
3A-(5), 3A-(6), 3A-(7), 3A-(8), and 3A-(9).
##STR00008## ##STR00009## ##STR00010##
[0030] wherein, in Formulae 3A-(1), 3A-(2), 3A-(3), 3A-(4), 3A-(5),
3A-(6), 3A-(7), 3A-(8), and 3A-(9): M may be platinum (Pt); and
R.sub.1a to R.sub.5a, R.sub.1b to R.sub.5b, R.sub.11a to R.sub.14a,
R.sub.11b to R.sub.14b, R.sub.21a to R.sub.28a, and R.sub.21b to
R.sub.28b each independently may be selected from the group of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a C.sub.1-C.sub.10 alkyl group, and a
C.sub.1-C.sub.20 alkoxy group, a substituted C.sub.1-C.sub.10 alkyl
group, a substituted C.sub.1-C.sub.20 alkoxy group, a phenyl group,
a naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, a triazinyl group,
and a substituted cyclic group that is substituted with at least
one selected from the group of: a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; the substituted C.sub.1-C.sub.10 alkyl group
and the substituted C.sub.1-C.sub.20 alkoxy group each may be
substituted with at least one selected from the group of a
deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a
nitro group, and an amino group; the substituted cyclic group may
be selected from the group of a substituted phenyl group, a
substituted naphthyl group, a substituted anthryl group, a
substituted fluorenyl group, a substituted carbazolyl group, a
substituted pyridinyl group, a substituted pyrimidinyl group, and a
substituted triazinyl group.
[0031] The organometallic compound may be represented by one
selected from the group of Formulae 3A-(1), 3A-(2), 3A-(4), 3A-(6),
3A-(8), and 3A-(9); and R.sub.1a=R.sub.1b, R.sub.2a=R.sub.2b,
R.sub.3a=R.sub.3b, R.sub.4a=R.sub.4b, R.sub.5a=R.sub.5b,
R.sub.11a=R.sub.11b, R.sub.12a=R.sub.12b, R.sub.13a=R.sub.13b,
R.sub.14a=R.sub.14b, R.sub.21a=R.sub.21b, R.sub.22a=R.sub.22b,
R.sub.23a=R.sub.23b, R.sub.24a=R.sub.24b, R.sub.25a=R.sub.25b,
R.sub.26a=R.sub.26b, R.sub.27a=R.sub.27b, and
R.sub.28a=R.sub.28b.
[0032] The organometallic compound may be represented by Formula
4-(a):
##STR00011##
[0033] wherein, in Formula 4-(a): M may be a transition metal;
X.sub.1a may be N or C(R.sub.5a); X.sub.1b may be N or C(R.sub.5b);
R.sub.2, to R.sub.5a and R.sub.2b to R.sub.5b each independently
may be selected from the group of a hydrogen atom, a deuterium
atom, a halogen atom, a hydroxyl group, a cyano group, a nitro
group, an amino group, an amidino group, a hydrazine, a hydrazone,
a carboxyl group or a salt thereof, a sulfonic acid group or a salt
thereof, a phosphoric acid group or a salt thereof, a substituted
or unsubstituted C.sub.1-C.sub.60 alkyl group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkenyl group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkynyl group, a substituted or
unsubstituted C.sub.1-C.sub.60 alkoxy group, a substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkenyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 heterocycloalkyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 heterocycloalkenyl
group, a substituted or unsubstituted C.sub.6-C.sub.60 aryl group,
a substituted or unsubstituted C.sub.6-C.sub.60 aryloxy group, a
substituted or unsubstituted C.sub.6-C.sub.60 arylthio group, a
substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5),
--C(.dbd.O)(Q.sub.6), and a binding site with an adjacent ligand
via a single bond or a divalent linking group; two substituents of
R.sub.2a to R.sub.5a may be optionally linked together to form at
least one selected from the group of a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 hetero alicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; two
substituents of R.sub.2b to R.sub.5b may be optionally linked
together to form at least one selected from the group of a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 hetero alicyclic
ring, a substituted or unsubstituted C.sub.6-C.sub.20 aromatic
ring, and a substituted or unsubstituted C.sub.2-C.sub.20
heteroaromatic ring; Q.sub.1 to Q.sub.6 each independently may be
selected from the group of a hydrogen atom, a substituted or
unsubstituted C.sub.1-C.sub.60 alkyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, and a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group; L may be an
organic ligand; m1 may be 0, 1, or 2; Y.sub.1 may be a single bond
or a divalent linking group including at least one selected from
the group of --O--, --S--, --N(Z.sub.1)--,
--[C(Z.sub.2)(Z.sub.3)].sub.a--, and
--[Si(Z.sub.4)(Z.sub.5)].sub.b--; Z.sub.1 to Z.sub.5 each
independently may be a hydrogen atom, a deuterium atom, a halogen
atom, a hydroxyl group, a cyano group, a nitro group, an amino
group, an amidino group, a hydrazine, a hydrazone, a carboxyl group
or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.60 alkyl
group, a C.sub.1-C.sub.60 alkyl group substituted with at least one
halogen atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60
alkynyl group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, or a
C.sub.2-C.sub.60 heteroaryl group, and a and b are each
independently an integer from 1 to 4.
[0034] Y.sub.1 may be --N(Z.sub.1)--; Z.sub.1 may be at least one
selected from the group of a phenyl group, a naphthyl group, an
anthryl group, a fluorenyl group, a carbazolyl group, a pyridinyl
group, a pyrimidinyl group, a triazinyl group, and a substituted
cyclic group that is substituted with at least one selected from
the group of: a deuterium atom, a halogen atom, a hydroxyl group, a
cyano group, a nitro group, an amino group, a C.sub.1-C.sub.20
alkyl group, a C.sub.1-C.sub.10 alkoxy group, a phenyl group, a
naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, and a triazinyl
group; and the substituted cyclic group may be selected from the
group of a substituted phenyl group, a substituted naphthyl group,
a substituted anthryl group, a substituted fluorenyl group, a
substituted carbazolyl group, a substituted pyridinyl group, a
substituted pyrimidinyl group, and a substituted triazinyl
group.
[0035] n may be 3, and m may be 0.
[0036] n may be 1, and m may be an integer from 1 to 4.
[0037] The organometallic compound may be represented by one
selected from the group of Formulae 5 to 8:
##STR00012##
[0038] wherein, in Formulae 5 to 8: M, X.sub.1, R.sub.1 to R.sub.5,
and L may be as above in Formula 1; m2 may be 0, 1, or 2; X.sub.12
and X.sub.16d each independently may be N or C; X.sub.21 may be N
or C(R.sub.51), X.sub.22 may be N or C(R.sub.52), X.sub.23 may be N
or C(R.sub.53), X.sub.24 may be N or C(R.sub.54), X.sub.25 may be N
or C(R.sub.55), X.sub.26 may be N or C(R.sub.56), X.sub.27 may be N
or C(R.sub.57), X.sub.28 may be N or C(R.sub.58), and X.sub.29 may
be N or C(R.sub.59); R.sub.41, R.sub.42, and R.sub.51 to R.sub.59
each independently may be selected from the group of a hydrogen
atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano
group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a substituted or unsubstituted C.sub.1-C.sub.60 alkyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkenyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkynyl
group, a substituted or unsubstituted C.sub.1-C.sub.60 alkoxy
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkenyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryloxy group, a substituted or
unsubstituted C.sub.6-C.sub.60 arylthio group, a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.11)(Q.sub.12), --Si(Q.sub.13)(Q.sub.14)(Q.sub.15), and a
binding site with an adjacent ligand via a single bond or a
divalent linking group; two adjacent substituents of R.sub.41,
R.sub.42, and R.sub.51 to R.sub.59 may be optionally linked
together to form one selected from the group of a substituted or
unsubstituted C.sub.4-C.sub.20 alicyclic ring, a substituted or
unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring, a substituted
or unsubstituted C.sub.6-C.sub.20 aromatic ring, and a substituted
or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; and Q.sub.11
to Q.sub.15 each independently may be selected from the group of a
hydrogen atom, a C.sub.1-C.sub.10 alkyl group, a C.sub.6-C.sub.20
aryl group, and a C.sub.2-C.sub.20 heteroaryl group.
[0039] The organometallic compound may be represented by one
selected from the group of Formulae 5-(1), 5-(2), 5-(3), and
5-(4):
##STR00013##
[0040] wherein, in Formulae 5-(1) to 5-(4): M, X.sub.1, R.sub.1 to
R.sub.5, and L may be as in Formula 1; m2 may be 0, 1, or 2;
X.sub.21 may be N or C(R.sub.51), X.sub.22 may be N or C(R.sub.52),
X.sub.23 may be N or C(R.sub.53), X.sub.24 may be N or C(R.sub.54),
X.sub.25 may be N or C(R.sub.55), and X.sub.26 may be N or
C(R.sub.56); and R.sub.41, R.sub.51 to R.sub.56, R.sub.61 to
R.sub.68, and R.sub.71 to R.sub.74 each independently may be
selected from the group of a hydrogen atom, a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.20 alkyl
group, a C.sub.1-C.sub.20 alkoxy group, a substituted
C.sub.1-C.sub.20 alkyl group, a substituted C.sub.1-C.sub.20 alkoxy
group, a phenyl group, a naphthyl group, an anthryl group, a
fluorenyl group, a carbazolyl group, a pyridinyl group, a
pyrimidinyl group, a triazinyl group, and a substituted cyclic
group that is substituted with at least one selected from the group
of: a deuterium atom, a halogen atom, a hydroxyl group, a cyano
group, a nitro group, an amino group, a C.sub.1-C.sub.20 alkyl
group, a C.sub.1-C.sub.20 alkoxy group, a phenyl group, a naphthyl
group, an anthryl group, a fluorenyl group, a carbazolyl group, a
pyridinyl group, a pyrimidinyl group, and a triazinyl group; the
substituted C.sub.1-C.sub.20 alkyl group and the substituted
C.sub.1-C.sub.20 alkoxy group each may be substituted with at least
one selected from the group of a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, and an amino group;
and the substituted cyclic group may be selected from the group of
a substituted phenyl group, a substituted naphthyl group, a
substituted anthryl group, a substituted fluorenyl group, a
substituted carbazolyl group, a substituted pyridinyl group, a
substituted pyrimidinyl group, and a substituted triazinyl
group.
[0041] The organometallic compound may be represented by one
selected from the group of Formulae 5-(a), 6-(a), and 7-(a):
##STR00014##
[0042] wherein, in Formulae 5-(a), 6-(a), and 7-(a): M, X.sub.1,
R.sub.2 to R.sub.5, and L may be as in Formula 1; m2 may be 0, 1,
or 2; X.sub.12 may be C or N; X.sub.21 may be N or C(R.sub.51),
X.sub.22 may be N or C(R.sub.52), X.sub.23 may be N or C(R.sub.53),
X.sub.24 may be N or C(R.sub.54), X.sub.25 may be N or C(R.sub.55),
X.sub.26 may be N or C(R.sub.56), and X.sub.27 may be N or
C(R.sub.57); R.sub.41 and R.sub.51 to R.sub.57 each independently
may be selected from the group of a hydrogen atom, a deuterium
atom, a halogen atom, a hydroxyl group, a cyano group, a nitro
group, an amino group, an amidino group, a hydrazine, a hydrazone,
a carboxyl group or a salt thereof, a sulfonic acid group or a salt
thereof, a phosphoric acid group or a salt thereof, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkyl group
substituted with at least one fluorine atom, a C.sub.1-C.sub.20
alkoxy group, a phenyl group, a naphthyl group, and an anthryl
group;
[0043] Y.sub.2 may be a single bond or a divalent linking group
including at least one selected from the group of --O--, --S--,
--N(Z.sub.11)--, --[C(Z.sub.12)(Z.sub.13)].sub.c--, and
--[Si(Z.sub.14)(Z.sub.15)].sub.d--;
[0044] Z.sub.11 to Z.sub.15 each independently may be selected from
the group of a hydrogen atom, a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, C.sub.1-C.sub.60 alkyl group, a
C.sub.1-C.sub.60 alkyl group substituted with at least one halogen
atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60 alkynyl
group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, or a
C.sub.2-C.sub.60 heteroaryl group; and c and d each independently
may be an integer from 1 to 4.
[0045] The organometallic compound may be one selected from the
group of compounds 1 to 68:
##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##
##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024##
##STR00025## ##STR00026## ##STR00027## ##STR00028##
##STR00029##
[0046] wherein, in compounds 60-62, Ph may be a phenyl group and Me
may be a methyl group.
[0047] Embodiments are also directed to an organic light-emitting
device, including: a substrate; a first electrode; a second
electrode opposite the first electrode; and an organic layer
between the first electrode and the second electrode, the organic
layer including the organometallic compound.
[0048] The organic layer may include at least one selected from the
group of a hole injection layer, a hole transport layer, a
functional layer having both hole injection and hole transport
capabilities, a buffer layer, an electron blocking layer, an
emission layer, a hole blocking layer, an electron transport layer,
an electron injection layer, and a functional layer having both
electron injection and electron transport capabilities.
[0049] The organic layer may include an emission layer; the
organometallic compound may be in the emission layer; and light may
be emitted from the emission layer based on a phosphorescence
mechanism.
[0050] The organometallic compound in the emission layer may serve
as a dopant; and the emission layer may include a carbazole-based
compound as a host.
[0051] The carbazole-based compound may be represented by Formula
10:
##STR00030##
[0052] wherein, in Formula 10: Ar.sub.1 may be selected from the
group of a substituted or unsubstituted C.sub.1-C.sub.60 alkylene
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkenylene
group, --C(.dbd.O)--, --N(R.sub.100)--, a substituted or
unsubstituted C.sub.6-C.sub.60 arylene group, and a substituted or
unsubstituted C.sub.2-C.sub.60 heteroarylene group; R.sub.100 may
be selected from the group of a substituted or unsubstituted
C.sub.6-C.sub.60 aryl group, and a substituted or unsubstituted
C.sub.2-C.sub.60 heteroaryl group; p may be an integer from 0 to
10; R.sub.91 to R.sub.96 each independently may be selected from
the group of a hydrogen atom, a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a substituted or unsubstituted
C.sub.1-C.sub.60 alkyl group, a substituted or unsubstituted
C.sub.2-C.sub.60 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.60 alkynyl group, a substituted or unsubstituted
C.sub.1-C.sub.60 alkoxy group, a substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 cycloalkenyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 heterocycloalkenyl group, a
substituted or unsubstituted C.sub.6-C.sub.60 aryl group, a
substituted or unsubstituted C.sub.6-C.sub.60 aryloxy group, a
substituted or unsubstituted C.sub.6-C.sub.60 arylthio group, and a
substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl group;
[0053] two adjacent substituents of R.sub.91 to R.sub.96 optionally
may be linked together to form one selected from the group of a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic group, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic
group, a substituted or unsubstituted C.sub.6-C.sub.20 aromatic
ring, and a substituted or unsubstituted C.sub.2-C.sub.20
heteroaromatic ring; and
[0054] q, r, s, t, u, and v each independently may be an integer
from 1 to 4.
[0055] The carbazole-based compound may be one selected from the
group of compounds H1 to H30:
##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035##
##STR00036## ##STR00037## ##STR00038##
[0056] The organic layer may include at least one selected from the
group of a hole injection layer, a hole transport layer, and a
functional layer having both hole injection and hole transport
capabilities; and the at least one of the hole injection layer, the
hole transport layer, and the functional layer having both hole
injection and hole transport capabilities may include a
charge-generating material.
[0057] The organic layer may include an electron transport layer,
and the electron transport layer may include a metal-containing
material.
BRIEF DESCRIPTION OF THE DRAWING
[0058] Features will become apparent to those of ordinary skill in
the art by describing in detail exemplary embodiments with
reference to the attached drawing in which FIG. 1 schematically
illustrates the structure of an organic light-emitting device
according to an embodiment.
DETAILED DESCRIPTION
[0059] Example embodiments will now be described more fully
hereinafter with reference to the accompanying drawing; however,
they may be embodied in different forms and should not be construed
as limited to the embodiments set forth herein. Rather, these
embodiments are provided so that this disclosure will be thorough
and complete, and will fully convey exemplary implementations to
those skilled in the art.
[0060] In the drawing FIGURES, the dimensions of layers and regions
may be exaggerated for clarity of illustration. It will also be
understood that when a layer is referred to as being "between" two
layers, it can be the only layer between the two layers, or one or
more intervening layers may also be present. Like reference
numerals refer to like elements throughout.
[0061] As used herein, the term "and/or" includes any and all
combinations of one or more of the associated listed items.
Expressions such as "at least one of," and "selected from the group
of," when preceding a list of elements, modify the entire list of
elements and do not modify the individual elements of the list.
[0062] According to an embodiment, there is provided an
organometallic compound represented by Formula 1:
##STR00039##
[0063] In Formula 1 above, M may be a transition metal.
[0064] For example, M may be a Group VI metal, a Group VII metal, a
Group VIII metal, a Group IX metal, or a Group X metal, a Group XI
metal, or the like. In an embodiment, M in Formula 1 may be
ruthenium (Ru), rhodium (Rh), palladium (Pd), tungsten (W), rhenium
(Re), osmium (Os), iridium (Ir), platinum (Pt), and the like.
[0065] In Formula 1, X.sub.1 may be N or C(R.sub.5).
[0066] In Formula 1, R.sub.1 to R.sub.5 each independently may be a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a substituted or unsubstituted C.sub.1-C.sub.60 alkyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkenyl
group, a substituted or unsubstituted C.sub.2-C.sub.60 alkynyl
group, a substituted or unsubstituted C.sub.1-C.sub.60 alkoxy
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkyl group, a substituted or unsubstituted
C.sub.3-C.sub.10 heterocycloalkenyl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group, a substituted or
unsubstituted C.sub.6-C.sub.60 aryloxy group, a substituted or
unsubstituted C.sub.6-C.sub.60 arylthio group, a substituted or
unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5),
--C(.dbd.O)(Q.sub.6) (where Q.sub.1 to Q.sub.6 each independently
may be a hydrogen atom, a substituted or unsubstituted
C.sub.1-C.sub.60 alkyl group, a substituted or unsubstituted
C.sub.6-C.sub.60 aryl group, or a substituted or unsubstituted
C.sub.2-C.sub.60 heteroaryl group), or a binding site with an
adjacent ligand via a single bond or a divalent linking group.
[0067] In Formula 1, R.sub.1 to R.sub.5 each independently may be
one selected from the group of:
[0068] a hydrogen atom, a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof;
[0069] a C.sub.1-C.sub.60 alkyl group, a C.sub.2-C.sub.60 alkenyl
group, a C.sub.2-C.sub.60 alkynyl group, a C.sub.1-C.sub.60 alkoxy
group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.3-C.sub.10
cycloalkenyl group, a C.sub.3-C.sub.10 heterocycloalkyl group, a
C.sub.3-C.sub.10 heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl
group, a C.sub.6-C.sub.60 aryloxy group, a C.sub.6-C.sub.60
arylthio group, and a C.sub.2-C.sub.60 heteroaryl group;
[0070] a C.sub.1-C.sub.60 alkyl group, a C.sub.2-C.sub.60 alkenyl
group, a C.sub.2-C.sub.60 alkynyl group, a C.sub.1-C.sub.60 alkoxy
group, a C.sub.3-C.sub.10 cycloalkyl group, a C.sub.3-C.sub.10
cycloalkenyl group, a C.sub.3-C.sub.10 heterocycloalkyl group, a
C.sub.3-C.sub.10 heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl
group, a C.sub.6-C.sub.60 aryloxy group, a C.sub.6-C.sub.60
arylthio group, and a C.sub.2-C.sub.60 heteroaryl group that may be
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a C.sub.1-C.sub.60 alkyl group, a
C.sub.1-C.sub.60 alkyl group substituted with at least one halogen
atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60 alkynyl
group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, a
C.sub.6-C.sub.60 aryloxy group, a C.sub.6-C.sub.60 arylthio group,
a C.sub.2-C.sub.60 heteroaryl group, --N(Q.sub.11)(Q.sub.12), and
--Si(Q.sub.13)(Q.sub.14)(Q.sub.15) (where Q.sub.11 to Q.sub.15 are
each independently a hydrogen atom, a C.sub.1-C.sub.10 alkyl group,
a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20 heteroaryl
group);
[0071] --N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5), and
--C(.dbd.O)(Q.sub.6) (where Q.sub.1 to Q.sub.6 each independently
may be a hydrogen atom, a C.sub.1-C.sub.60 alkyl group, a
C.sub.6-C.sub.60 aryl group, or a C.sub.2-C.sub.60 heteroaryl
group); and
[0072] a binding site with an adjacent ligand via a single bond or
a divalent linking group.
[0073] In an embodiment, in Formula 1, R.sub.1 to R.sub.5 each
independently may be, for example, one selected from the group
of:
[0074] a hydrogen atom, a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof;
[0075] a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy
group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl
group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl
group, a cyclohexenyl group, a cyclopentadienyl group, a
cyclohexadienyl group, a phenyl group, a naphthyl group, an anthryl
group, a fluorenyl group, a chrysenyl group, a pyrenyl group, a
phenanthrenyl group, a pyrrolyl group, a pyridinyl group, a
pyrimidinyl group, a pyrazinyl group, a triazinyl group, a
carbazolyl group, an indolyl group, a benzoimidazolyl group, a
quinolinyl group, an isoquinolinyl group;
[0076] a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy
group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl
group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl
group, a cyclohexenyl group, a cyclopentadienyl group, a
cyclohexadienyl group, a phenyl group, a naphthyl group, an anthryl
group, a fluorenyl group, a chrysenyl group, a pyrenyl group, a
phenanthrenyl group, a pyrrolyl group, a pyridinyl group, a
pyrimidinyl group, a pyrazinyl group, a triazinyl group, a
carbazolyl group, an indolyl group, a benzoimidazolyl group, a
quinolinyl group, and an isoquinolinyl group that may be
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a C.sub.1-C.sub.20 alkyl group, a
C.sub.1-C.sub.20 alkoxy group, a phenyl group, a naphthyl group, an
anthryl group, a dimethyl-fluorenyl group, and a phenyl-carbazolyl
group;
[0077] --N(Q.sub.1)(Q.sub.2), --Si(Q.sub.3)(Q.sub.4)(Q.sub.5),
--C(.dbd.O)(Q.sub.6) (where Q.sub.1 to Q.sub.6 are each
independently a hydrogen atom, a C.sub.1-C.sub.20 alkyl group, a
phenyl group, a naphthyl group, or an anthryl group); and
[0078] a binding site with an adjacent ligand via a single bond or
a divalent linking group.
[0079] In an embodiment, X.sub.1 in Formula 1 may be C(R.sub.5);
and R.sub.1 to R.sub.5 each independently may be one of, e.g., a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof; a methyl group, an ethyl group, an n-propyl group, an
i-propyl group, an n-butyl group, an i-butyl group, a t-butyl
group, a pentyl group, a hexyl group, a heptyl group, an octyl
group, a nonyl group, a decyl group, a methoxy group, an ethoxy
group, a propoxy group, a butoxy group, and pentoxy group; and a
methyl group, an ethyl group, an n-propyl group, an i-propyl group,
an n-butyl group, an i-butyl group, a t-butyl group, a pentyl
group, a hexyl group, a heptyl group, an octyl group, a nonyl
group, a decyl group, a methoxy group, an ethoxy group, a propoxy
group, a butoxy group, and a pentoxy group that may be substituted
with at least one of a deuterium atom, --F, a hydroxyl group, a
cyano group, a nitro group, and an amino group.
[0080] In an embodiment, X.sub.1 in Formula 1 may be N; and R.sub.1
to R.sub.4 each independently may be one of a hydrogen atom, a
deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a
nitro group, an amino group, an amidino group, a hydrazine, a
hydrazone, a carboxyl group or a salt thereof, a sulfonic acid
group or a salt thereof, a phosphoric acid group or a salt thereof;
a methyl group, an ethyl group, an n-propyl group, an i-propyl
group, an n-butyl group, an i-butyl group, a t-butyl group, a
pentyl group, a hexyl group, a heptyl group, an octyl group, a
nonyl group, a decyl group, a methoxy group, an ethoxy group, a
propoxy group, a butoxy group, and pentoxy group; and a methyl
group, an ethyl group, an n-propyl group, an i-propyl group, an
n-butyl group, an i-butyl group, a t-butyl group, a pentyl group, a
hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl
group, a methoxy group, an ethoxy group, a propoxy group, a butoxy
group, and a pentoxy group that may be substituted with at least
one of a deuterium atom, --F, a hydroxyl group, a cyano group, a
nitro group, and an amino group.
[0081] In an embodiment, in Formula 1, X.sub.1 may be C(R.sub.5);
and R.sub.1 to R.sub.5 each independently may be a hydrogen atom, a
methyl group, an ethyl group, an n-propyl group, a i-propyl group,
an n-butyl group, an i-butyl group, a t-butyl group, a methoxy
group, an ethoxy group, a propoxy group, a butoxy group, a pentoxyl
group, or --CF.sub.3. In some other embodiments, in Formula 1,
X.sub.1 may be N; and R.sub.1 to R.sub.4 each independently may be
a hydrogen atom, a methyl group, an ethyl group, an n-propyl group,
a i-propyl group, an n-butyl group, an i-butyl group, a t-butyl
group, a methoxy group, an ethoxy group, a propoxy group, a butoxy
group, a pentoxyl group, or --CF.sub.3.
[0082] In Formula 1, two substituents of R.sub.1 to R.sub.5 may be
optionally linked together to form a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, or a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring.
[0083] In an embodiment, i) R.sub.2 and R.sub.3 may be linked
together so that the organometallic compound may be represented by
Formula 1A below; ii) X.sub.1 may be C(R.sub.5), and R.sub.5 and
R.sub.4 may be linked together so that the organometallic compound
may be represented by Formula 1B below; or iii) R.sub.2 and R.sub.3
may be linked together, X.sub.1 may be C(R.sub.5), and R.sub.5 and
R.sub.4 may be linked together so that the organometallic compound
may be represented by Formula 1C below:
##STR00040##
[0084] In Formulae 1A, 1B, and 1C, M, X.sub.1, and R.sub.1 to
R.sub.5 may be the same as set forth above, and n, L, and m may be
as set forth below.
[0085] In Formulae 1A, 1B, and 1C above, the A ring and the B ring
each independently may be a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, or a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring.
[0086] For example, in Formulae 1A and 1C, the A ring may be at
least one of benzene, pentalene, indene, naphthalene, azulene,
heptalene, indacene, acenaphthylene, fluorene, spiro-fluorene,
phenalene, phenanthrene, anthracene, fluoranthene, triphenylene,
pyrene, and chrysene; and benzene, pentalene, indene, naphthalene,
azulene, heptalene, indacene, acenaphthylene, fluorene,
spiro-fluorene, phenalene, phenanthrene, anthracene, fluoranthene,
triphenylene, pyrene, and chrysene that may be substituted with at
least one of a deuterium atom, a halogen atom, a hydroxyl group, a
cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a C.sub.1-C.sub.60 alkyl group, a C.sub.1-C.sub.60
alkyl group substituted with at least one halogen atom, a
C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60 alkynyl group, a
C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10 cycloalkyl group,
a C.sub.3-C.sub.10 cycloalkenyl group, a C.sub.3-C.sub.10
heterocycloalkyl group, a C.sub.3-C.sub.10 heterocycloalkenyl
group, a C.sub.6-C.sub.60 aryl group, a C.sub.6-C.sub.60 aryloxy
group, a C.sub.6-C.sub.60 arylthio group, a C.sub.2-C.sub.60
heteroaryl group, --N(Q.sub.11)(Q.sub.12), and
--Si(Q.sub.13)(Q.sub.14)(Q.sub.15) (where Q.sub.11 to Q.sub.15 are
each independently a hydrogen atom, a C1-C10 alkyl group, a
C.sub.6-C.sub.2O aryl group or a C.sub.2-C.sub.2O heteroaryl
group).
[0087] For example, in Formulae 1B and 1C, the B ring may be at
least one of, e.g., cyclopropane, cyclobutane, cyclopentane,
cyclohexane, cycloheptane, cyclooctane, cyclopentene,
cyclopentadiene, cyclohexadiene, cycloheptadiene, bicyclo-heptane,
bicyclo-octane, benzene, pentalene, indene, naphthalene, azulene,
heptalene, indacene, acenaphthylene, fluorene, spiro-fluorene,
phenalene, phenanthrene, anthracene, fluoranthene, triphenylene,
pyrene, and chrysene; and cyclopropane, cyclobutane, cyclopentane,
cyclohexane, cycloheptane, cyclooctane, cyclopentene,
cyclopentadiene, cyclohexadiene, cycloheptadiene, bicyclo-heptane,
bicyclo-octane, benzene, pentalene, indene, naphthalene, azulene,
heptalene, indacene, acenaphthylene, fluorene, spiro-fluorene,
phenalene, phenanthrene, anthracene, fluoranthene, triphenylene,
pyrene, and chrysene that are substituted with at least one of a
deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a
nitro group, an amino group, an amidino group, a hydrazine, a
hydrazone, a carboxyl group or a salt thereof, a sulfonic acid
group or a salt thereof, a phosphoric acid group or a salt thereof,
a C.sub.1-C.sub.60 alkyl group, a C.sub.1-C.sub.60 alkyl group
substituted with at least one halogen atom, a C.sub.2-C.sub.60
alkenyl group, a C.sub.2-C.sub.60 alkynyl group, a C.sub.1-C.sub.60
alkoxy group, a C.sub.3-C.sub.10 cycloalkyl group, a
C.sub.3-C.sub.10 cycloalkenyl group, a C.sub.3-C.sub.10
heterocycloalkyl group, a C.sub.3-C.sub.10 heterocycloalkenyl
group, a C.sub.6-C.sub.60 aryl group, a C.sub.6-C.sub.60 aryloxy
group, a C.sub.6-C.sub.60 arylthio group, a C.sub.2-C.sub.60
heteroaryl group, --N(Q.sub.11)(Q.sub.12), and
--Si(Q.sub.13)(Q.sub.14)(Q.sub.15) (where Q.sub.11 to Q.sub.15 each
independently may be a hydrogen atom, a C.sub.1-C.sub.10 alkyl
group, a C.sub.6-C.sub.20 aryl group, or a C.sub.2-C.sub.20
heteroaryl group).
[0088] In an embodiment, the organometallic compound may be
represented by Formula 1A-(1), 1B-(1), 1B-(2), 1B-(3), 1C-(1),
1C-(2), 1C-(3), or 1D-(1) below:
##STR00041## ##STR00042##
[0089] In Formulae 1A-(1), 1B-(1), 1B-(2), 1B-(3), 1C-(1), 1C-(2),
1C-(3), and 1D-(1), M, and R.sub.1 to R.sub.5 may be the same as
set forth above; n, L and m may be the same as set forth below; and
R.sub.11 to R.sub.14, and R.sub.21 to R.sub.28 may be the same as
R.sub.1 to R.sub.5 set forth above.
[0090] For example, in Formulae 1A-(1), 1B-(1), 1B-(2), 1B-(3),
1C-(1), 1C-(2), 1C-(3), and 1D-(1) above, M may be a transition
metal (for example, osmium (Os), iridium (Ir), or platinum (Pt));
R.sub.1 to R.sub.5, R.sub.11 to R.sub.14, and R.sub.21 to R.sub.28
each independently may be a hydrogen atom, a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.20 alkyl
group, and a C.sub.1-C.sub.20 alkoxy group; a C.sub.1-C.sub.20
alkyl group and a C.sub.1-C.sub.20 alkoxy group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, and an amino group;
a phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; and a phenyl group, a naphthyl group, an
anthryl group, a fluorenyl group, a carbazolyl group, a pyridinyl
group, a pyrimidinyl group, and a triazinyl group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, an amino group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; n may be an integer from 1 to 3; L may be an
organic ligand; and m may be an integer from 0 to 4.
[0091] In Formula 1 above, n may be an integer from 1 to 3. That
is, Formula 1 above may include one, two, or three ligands
represented by Formula 1':
##STR00043##
[0092] In Formula 1', * indicates a binding site with M in Formula
1.
[0093] Accordingly, the organometallic compound may include the
ligand represented by Formula 1'.
[0094] If n is 2 or greater, at least two ligands represented by
Formula 1' may be the same or different.
[0095] In Formula 1, L may be an organic ligand, and m may indicate
the number of L's, and may be an integer from 0 to 4. L may be a
monodentate ligand, bidentate ligand, a tridentate ligand, or a
tetradentate ligand. When m is 0, the organometallic compound may
include only the ligand represented by Formula 1'. If m is 2 or
greater, at least two L may be the same or different.
[0096] L may be a suitable organic ligand, e.g., a ligand that does
not undesirably change chemical and physical characteristics of the
organometallic compound.
[0097] For example, L in Formula 1 may include at least one of the
ligands represented by Formulae 2A to 2F below.
##STR00044##
[0098] In Formula 2B, M.sub.1 may be P or As.
[0099] In Formulae 2A to 2F, X.sub.1la, X.sub.11b, X.sub.12,
X.sub.13, X.sub.14, X.sub.15, X.sub.16a, X.sub.16b, X.sub.16c,
X.sub.16d, X.sub.16e, X.sub.16f, X.sub.16g, X.sub.17a, X.sub.17b,
X.sub.17c and X.sub.17d each independently may be C, N, O,
N(R.sub.35), P(R.sub.36)(R.sub.37), or As(R.sub.38)(R.sub.39);
R.sub.33'' and R.sub.34'' each independently may be a single bond,
a substituted or unsubstituted C.sub.1-C.sub.5 alkylene group (for
example, methylene, ethylene, or the like), or a substituted or
unsubstituted C.sub.2-C.sub.5 alkenylene group (for example,
ethenylene or the like); R.sub.31, R.sub.32a, R.sub.32b, R.sub.32c,
R.sub.33a, R.sub.33b, R.sub.34, R.sub.35, R.sub.36, R.sub.37,
R.sub.38, and R.sub.39 each independently may be a hydrogen atom, a
deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a
nitro group, an amino group, an amidino group, a hydrazine, a
hydrazone, a carboxyl group or a salt thereof, a sulfonic acid
group or a salt thereof, a phosphoric acid group or a salt thereof,
a substituted or unsubstituted C.sub.1-C.sub.60 alkyl group, a
substituted or unsubstituted C.sub.2-C.sub.60 alkenyl group, a
substituted or unsubstituted C.sub.2-C.sub.60 alkynyl group, a
substituted or unsubstituted C.sub.1-C.sub.60 alkoxy group, a
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 heterocycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkenyl group, a substituted or unsubstituted
C.sub.6-C.sub.60 aryl group, or a substituted or unsubstituted
C.sub.2-C.sub.60 heteroaryl group; the C ring, the D ring, the E
ring, the F ring, the G ring, and the H ring each independently may
be a 5-membered to 20-membered saturated ring, or a 5-membered or
20-membered unsaturated ring; and * may indicate a binding site
with M in Formula 1.
[0100] In Formulae 2A to 2F, R.sub.31, R.sub.32a, R.sub.32b,
R.sub.32c, R.sub.33a, R.sub.33b, R.sub.34, R.sub.35, R.sub.36,
R.sub.37, R.sub.38, and R.sub.39 each independently may be one of a
hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a C.sub.1-C.sub.20 alkyl group, and a
C.sub.1-C.sub.20 alkoxy group; a C.sub.1-C.sub.20 alkyl group and a
C.sub.1-C.sub.20 alkoxy group that are substituted with at least
one of a deuterium atom, a halogen atom, a hydroxyl group, a cyano
group, a nitro group, and an amino group; a phenyl group, a
naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, and a triazinyl
group; and a phenyl group, a naphthyl group, an anthryl group, a
fluorenyl group, a carbazolyl group, a pyridinyl group, a
pyrimidinyl group, and a triazinyl group that are substituted with
at least one of a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, a C.sub.1-C.sub.20
alkyl group, a C.sub.1-C.sub.20 alkoxy group, a phenyl group, a
naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, and a triazinyl
group.
[0101] For example, if m is 1 or greater in Formula 1 above, L may
include a ligand represented by Formula 2C above, wherein X.sub.11a
and X.sub.11b in Formula 2C each independently may be, e.g., O,
P(R.sub.36)(R.sub.37), or As(R.sub.38)(R.sub.39).
[0102] In some other embodiments, if m is 1 or greater in Formula 1
above, L may include at least one of the ligands represented by
Formulae 2D, 2E, and 2F, wherein the C ring, the D ring, the E
ring, the F ring, the G ring, and the H ring in Formulae 2D, 2E,
and 2F each independently may be a substituted or unsubstituted
benzene, a substituted or unsubstituted pentalene, a substituted or
unsubstituted indene, a substituted or unsubstituted naphthalene, a
substituted or unsubstituted azulene, a substituted or
unsubstituted heptalene, a substituted or unsubstituted indacene, a
substituted or unsubstituted acenaphthylene, a substituted or
unsubstituted fluorene, a substituted or unsubstituted
spiro-fluorene, a substituted or unsubstituted phenalene, a
substituted or unsubstituted phenanthrene, a substituted or
unsubstituted anthracene, a substituted or unsubstituted
fluoranthene, a substituted or unsubstituted triphenylene, a
substituted or unsubstituted pyrene, a substituted or unsubstituted
chrysene, a substituted or unsubstituted pyrrole, a substituted or
unsubstituted imidazole, a substituted or unsubstituted pyrazole, a
substituted or unsubstituted isothiazole, a substituted or
unsubstituted isoxazole, a substituted or unsubstituted pyridine, a
substituted or unsubstituted pyrazine, a substituted or
unsubstituted pyrimidine, a substituted or unsubstituted
pyridazine, a substituted or unsubstituted isoindole, a substituted
or unsubstituted indole, a substituted or unsubstituted indazole, a
substituted or unsubstituted purine, a substituted or unsubstituted
isoquinoline, a substituted or unsubstituted quinoline, a
substituted or unsubstituted phthalazine, a substituted or
unsubstituted quinoxaline, a substituted or unsubstituted
quinazoline, or a substituted or unsubstituted cinnoline.
[0103] In this regard, i) when the C ring includes at least two
substituents (i.e., is substituted with at least two substituents),
adjacent two of the at least two substituents may be optionally
linked together to form a substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, a substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, a substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, or a substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; ii) when the D
ring includes at least two substituents (i.e., is substituted with
at least two substituents), adjacent two of the at least two
substituents my be optionally linked together to form a substituted
or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a substituted or
unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring, a substituted
or unsubstituted C.sub.6-C.sub.20 aromatic ring, or a substituted
or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring; iii) when
the E ring includes at least two substituents (i.e., is substituted
with at least two substituents), adjacent two of the at least two
substituents may be optionally linked together to form a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
a substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, or a
substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring;
iv) when the F ring includes at least two substituents (i.e., is
substituted with at least two substituents), adjacent two of the at
least two substituents may be optionally linked together to form a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
a substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, or a
substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring;
v) when the G ring includes at least two substituents (i.e., is
substituted with at least two substituents), adjacent two of the at
least two substituents may be optionally linked together to form a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
a substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, or a
substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic ring;
vi) when the H ring includes at least two substituents (i.e., is
substituted with at least two substituents), adjacent two of the at
least two substituents may be optionally linked together to form a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
a substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, or a
substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic
ring;
[0104] The above description of the B ring (in Formulae 1B and 1C)
may be used to describe "the substituted or unsubstituted
C.sub.4-C.sub.20 alicyclic ring, the substituted or unsubstituted
C.sub.2-C.sub.20 heteroalicyclic ring, the substituted or
unsubstituted C.sub.6-C.sub.20 aromatic ring, or the substituted or
unsubstituted C.sub.2-C.sub.20 heteroaromatic ring," set forth
above.
[0105] In an embodiment, if m is 1 or greater in Formula 1 above, L
may include at least one of the ligands represented by, e.g.,
Formulae 2A(1), 2B(1), 2C(1), and 2C(2):
##STR00045##
[0106] In Formulae 2A(1), 2B(1), 2C(1), and 2C(2), R.sub.32a,
R.sub.32b, R.sub.32c, R.sub.33a, R.sub.33b, R.sub.36, and R.sub.37
each independently may be as set forth above.
[0107] In Formula 1, n may be 2. Thus, the organometallic compound
may be represented by Formula 3 or 4 below.
##STR00046##
[0108] In Formulae 3 and 4, M and L may be as set forth above, and
m1 may be 0, 1, or 2.
[0109] In Formulae 3 and 4, X.sub.1a may be N or C(R.sub.5a);
X.sub.1b may be N or C(R.sub.5b); and the above-description of
R.sub.1 may be used to describe R.sub.1a to R.sub.5a, and R.sub.1b
to R.sub.5b.
[0110] In an embodiment, the organometallic compound may be
represented by Formula 3, wherein R.sub.1a=R.sub.1b,
R.sub.2a=R.sub.2b, R.sub.3a=R.sub.3b, R.sub.4a=R.sub.4b,
X.sub.1a=X.sub.1b, M=Pt, and m1=0, and may have a trans
structure.
[0111] In an embodiment, the organometallic compound may be
represented by Formula 4, wherein R.sub.1a=R.sub.1b,
R.sub.2a=R.sub.2b, R.sub.3a=R.sub.3b, R.sub.4a=R.sub.4B,
X.sub.1a=X.sub.1b, M=Pt, and m1=0, and may have a cis
structure.
[0112] In an embodiment, the organometallic compound may be
represented by Formula 3A-(1), 3A-(2), 3A-(3), 3A-(4), 3A-(5),
3A-(6), 3A-(7), 3A-(8), or 3A-(9) below.
##STR00047## ##STR00048##
[0113] In Formulae 3A-(1), 3A-(2), 3A-(3), 3A-(4), 3A-(5), 3A-(6),
3A-(7), 3A-(8), and 3A-(9), M may be platinum (Pt); and R.sub.1a to
R.sub.5a, R.sub.1b to R.sub.5b, R.sub.11a to R.sub.14a, R.sub.11b
to R.sub.14b, R.sub.21a to R.sub.28a, and R.sub.21b to R.sub.28b
each independently may be one of a hydrogen atom, a deuterium atom,
a halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.10 alkyl
group, and a C.sub.1-C.sub.20 alkoxy group; a C.sub.1-C.sub.20
alkyl group and a C.sub.1-C.sub.10 alkoxy group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, and an amino group;
a phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; and a phenyl group, a naphthyl group, an
anthryl group, a fluorenyl group, a carbazolyl group, a pyridinyl
group, a pyrimidinyl group, and a triazinyl group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, an amino group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group.
[0114] In an embodiment, in Formulae 3A-(1), 3A-(2), 3A-(3),
3A-(4), 3A-(5), 3A-(6), 3A-(7), 3A-(8), and 3A-(9), R.sub.1, to
R.sub.5a, R.sub.1b to R.sub.5b, R.sub.11a to R.sub.14a, R.sub.11b
to R.sub.14b, R.sub.21a to R.sub.28a, and R.sub.21b to R.sub.28b)
each independently may be, e.g., a hydrogen atom, a deuterium atom,
a halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.20 alkyl
group (for example, a methyl group, an ethyl group, an n-propyl
group, a i-propyl group, an n-butyl group, a i-butyl group, a
t-butyl group, a pentyl group, a hexyl group, a heptyl group, an
octyl group, a nonyl group, a decyl group, or the like), a
C.sub.1-C.sub.20 alkyl group substituted with at least one fluorine
atom (for example, --CF.sub.3), a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, or an anthryl group.
[0115] For example, the organometallic compound may be represented
by Formula 3A-(1), 3A-(2), 3A-(4), 3A-(6), 3A-(8), or 3A-(9),
wherein R.sub.1a=R.sub.1b, R.sub.2a=R.sub.2b), R.sub.3a=R.sub.3b,
R.sub.4a=R.sub.4b), R.sub.5a=R.sub.5b, R.sub.11a=R.sub.11b,
R.sub.12a=R.sub.12b, R.sub.13a=R.sub.13b, R.sub.14a=R.sub.14b,
R.sub.21a=R.sub.21b, R.sub.22a=R.sub.22b, R.sub.23a=R.sub.23b,
R.sub.24a=R.sub.24b, R.sub.25a=R.sub.25b, R.sub.26a=R.sub.26b,
R.sub.27a=R.sub.27b, and R.sub.28a=R.sub.28b.
[0116] The organometallic compound may be represented by Formula
4-(a) below.
##STR00049##
[0117] In Formula 4-(a), M and L may be as set forth above, and m1
may be 0, 1, or 2.
[0118] In Formula 4-(a), X.sub.1a may be N or C(R.sub.5a); X.sub.1b
may be N or C(R.sub.5b); and the above-description of R.sub.1 may
be used to describe R.sub.2a to R.sub.5a, and R.sub.1b to
R.sub.5b).
[0119] In Formula 4-(a), Y.sub.1 may be i) a divalent linking group
including at least one of --O--, --S--, --N(Z.sub.1)--,
--[C(Z.sub.2)(Z.sub.3)].sub.a--, and
--[Si(Z.sub.4)(Z.sub.5)].sub.b--, or ii) a single bond,
[0120] In --N(Z.sub.1)--, --[C(Z.sub.2)(Z.sub.3)].sub.a--, and
--[Si(Z.sub.4)(Z.sub.5)].sub.b--, Z.sub.1 to Z.sub.5 each
independently may be a hydrogen atom, a deuterium atom, a halogen
atom, a hydroxyl group, a cyano group, a nitro group, an amino
group, an amidino group, a hydrazine, a hydrazone, a carboxyl group
or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.60 alkyl
group, a C.sub.1-C.sub.60 alkyl group substituted with at least one
halogen atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60
alkynyl group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, or a
C.sub.2-C.sub.60 heteroaryl group, and a and b each independently
may be an integer from 1 to 4.
[0121] In an embodiment, in --N(Z.sub.1)--,
--[C(Z.sub.2)(Z.sub.3)].sub.a--, and
--[Si(Z.sub.4)(Z.sub.5)].sub.b--, Z.sub.1 to Z.sub.5 each
independently may be, e.g., a C.sub.1-C.sub.20 alkyl group (for
example, a methyl group, an ethyl group, an n-propyl group, a
i-propyl group, an n-butyl group, a i-butyl group, a t-butyl group,
a pentyl group, a hexyl group, a heptyl group, an octyl group, a
nonyl group, a decyl group, or the like), a C.sub.1-C.sub.20 alkyl
group substituted with at least --F (for example, --CF.sub.3), a
phenyl group, a naphthyl group, or an anthryl group, and a and b
each independently may be 1 or 2.
[0122] For example, in Formula 4-(a), Y.sub.1 may be
--N(Z.sub.1)--, wherein Z.sub.1 may be at least one of, e.g., a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; and a phenyl group, a naphthyl group, an
anthryl group, a fluorenyl group, a carbazolyl group, a pyridinyl
group, a pyrimidinyl group, and a triazinyl group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, an amino group, a
C.sub.1-C.sub.10 alkyl group, a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group.
[0123] In some other embodiments, the organometallic compound may
be an organometallic compound represented by Formula 1 with n=3 and
m=0. That is, the organometallic compound may include just three
ligands represented by Formula 1'. In an embodiment, in the
organometallic compound represented by Formula 1 with n=3 and m=0,
M may be Ir, and X.sub.1 and R.sub.1 to R.sub.4 may be as set forth
above.
[0124] In some other embodiments, the organometallic compound may
be an organometallic compound represented by Formula 1 wherein n=1
and m is an integer from 1 to 4.
[0125] In an embodiment, the organometallic compound represented by
Formula 1 wherein n=1 and m is an integer from 1 to 4 may be an
organometallic compound represented by, e.g., one of the Formulae 5
to 8 below:
##STR00050##
[0126] In Formulae 5 to 8, M, X1, R.sub.1 to R.sub.5, and L may be
as set forth above, and m2 may be 0, 1, or 2.
[0127] In Formulae 5 to 8, X.sub.12 and X.sub.16d each
independently may be N or C; and X.sub.21 may be N or C(R.sub.51);
X.sub.22 may be N or C(R.sub.52); X.sub.23 may be N or C(R.sub.53);
X.sub.24 may be N or C(R.sub.54); X.sub.25 may be N or C(R.sub.55);
X.sub.26 may be N or C(R.sub.56); X.sub.27 may be N or C(R.sub.57);
X.sub.28 may be N or C(R.sub.58); and X.sub.29 may be N or
C(R.sub.59); R.sub.41, R.sub.42, and R.sub.51 to R.sub.59 each
independently may be a hydrogen atom, a deuterium atom, a halogen
atom, a hydroxyl group, a cyano group, a nitro group, an amino
group, an amidino group, a hydrazine, a hydrazone, a carboxyl group
or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a substituted or
unsubstituted C.sub.1-C.sub.60 alkyl group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkenyl group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkynyl group, a substituted or
unsubstituted C.sub.1-C.sub.60 alkoxy group, a substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 cycloalkenyl group, a substituted or
unsubstituted C.sub.3-C.sub.10 heterocycloalkyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 heterocycloalkenyl
group, a substituted or unsubstituted C.sub.6-C.sub.60 aryl group,
a substituted or unsubstituted C.sub.6-C.sub.60 aryloxy group, a
substituted or unsubstituted C.sub.6-C.sub.60 arylthio group, a
substituted or unsubstituted C.sub.2-C.sub.60 heteroaryl group,
--N(Q.sub.11)(Q.sub.12), --Si(Q.sub.13)(Q.sub.14)(Q.sub.15) (where
Q.sub.11 to Q.sub.15 are each independently a hydrogen atom, a
C.sub.1-C.sub.10 alkyl group, a C.sub.6-C.sub.20 aryl group, or a
C.sub.2-C.sub.20 heteroaryl group), or a binding site with an
adjacent ligand via a single bond or divalent linking group,
wherein two adjacent substituents of R.sub.41, R.sub.42, and
R.sub.51 to R.sub.59 are optionally linked together to form a
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, a
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
a substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, or a
substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic
ring.
[0128] In Formulae 5 to 8, the above-description of R.sub.1 may be
used to describe R.sub.41, R.sub.42, and R.sub.51 to R.sub.59, and
the above-description of the B ring may be used to describe "the
substituted or unsubstituted C.sub.4-C.sub.20 alicyclic ring, the
substituted or unsubstituted C.sub.2-C.sub.20 heteroalicyclic ring,
the substituted or unsubstituted C.sub.6-C.sub.20 aromatic ring, or
the substituted or unsubstituted C.sub.2-C.sub.20 heteroaromatic
ring."
[0129] In an embodiment, the organometallic compound may be
represented by Formula 5-(1), 5-(2), 5-(3), or 5-(4) below:
##STR00051##
[0130] In Formulae 5-(1) to 5-(4), M, X.sub.1, R.sub.1 to R.sub.5,
L, m2, X.sub.21 to X.sub.26, R.sub.41, and R.sub.51 to R.sub.59 may
be as set forth above, and the above-description of R.sub.11 may be
used to describe R.sub.61 to R.sub.68, and R.sub.71 to
R.sub.74.
[0131] In an embodiment, in Formulae 5-(1) to 5-(4), X.sub.21 may
be N or C(R.sub.51); X.sub.22 may be N or C(R.sub.52); X.sub.23 may
be N or C(R.sub.53); X.sub.24 may be N or C(R.sub.54); X.sub.25 may
be N or C(R.sub.55); and X.sub.26 may be N or C(R.sub.56); R.sub.41
to R.sub.56, R.sub.61 to R.sub.68, and R.sub.71 to R.sub.74 each
independently may be, e.g., a hydrogen atom, a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, a C.sub.1-C.sub.20 alkyl
group, and a C.sub.1-C.sub.20 alkoxy group; a C.sub.1-C.sub.20
alkyl group and a C.sub.1-C.sub.10 alkoxy group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, and an amino group;
a phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group; and a phenyl group, a naphthyl group, an
anthryl group, a fluorenyl group, a carbazolyl group, a pyridinyl
group, a pyrimidinyl group, and a triazinyl group that are
substituted with at least one of a deuterium atom, a halogen atom,
a hydroxyl group, a cyano group, a nitro group, an amino group, a
C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxy group, a
phenyl group, a naphthyl group, an anthryl group, a fluorenyl
group, a carbazolyl group, a pyridinyl group, a pyrimidinyl group,
and a triazinyl group.
[0132] In some other embodiments, the organometallic compound may
be represented by Formula 5-(a), 6-(a), or 7-(a) below:
##STR00052##
[0133] In Formulae 5-(a), 6-(a), and 7-(a), M, X.sub.1, R.sub.2 to
R.sub.5, L, m2, X.sub.21 to X.sub.27, R.sub.41, and R.sub.51 to
R.sub.59 may be as set forth above. X.sub.12 may be C or N;
[0134] In Formulae 5-(a), 6-(a), and 7-(a), Y.sub.2 may be a single
bond or a divalent linking group including at least one of --O--,
--S--, --N(Z.sub.11)--, --[C(Z.sub.12)(Z.sub.13)]c-, and
--[Si(Z.sub.14)(Z.sub.15)]d-, wherein Z.sub.11 to Z.sub.15 each
independently may be, e.g., a hydrogen atom, a deuterium atom, a
halogen atom, a hydroxyl group, a cyano group, a nitro group, an
amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl
group or a salt thereof, a sulfonic acid group or a salt thereof, a
phosphoric acid group or a salt thereof, C.sub.1-C.sub.60 alkyl
group, a C.sub.1-C.sub.60 alkyl group substituted with at least one
halogen atom, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60
alkynyl group, a C.sub.1-C.sub.60 alkoxy group, a C.sub.3-C.sub.10
cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl group, a
C.sub.3-C.sub.10 heterocycloalkyl group, a C.sub.3-C.sub.10
heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl group, or a
C.sub.2-C.sub.60 heteroaryl group, and c and d each independently
may be an integer from 1 to 4.
[0135] The organometallic compound may be, for example, one of
Compounds 1 to 68 below:
##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057##
##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062##
##STR00063## ##STR00064## ##STR00065## ##STR00066##
[0136] In the organometallic compound of Formula 1, R.sub.1 may be
located between a first nitrogen and a second nitrogen, and thus
the R.sub.1 may have acidic characteristics (as illustrated in
Formula1'' below), which may allow for improved thermal
stability.
##STR00067##
[0137] For example, in the organometallic compound represented by
Formula 3, R.sub.1a may be located between a first nitrogen and a
second nitrogen, and thus the organometallic compound may have
acidic characteristics, thereby allowing for the formation of an
intermolecular hydrogen bond with a third nitrogen of an adjacent
ligand (as illustrated in Formula 3'' below).
##STR00068##
[0138] Therefore, the organometallic compounds according to one or
more of the above embodiments may have improved thermal stability.
Accordingly, an organic light-emitting device including the
organometallic compounds according to one or more of the above
embodiments may have improved properties (e.g., a low driving
voltage, a high luminance, a high efficiency, a long lifetime, and
the like).
[0139] The organometallic compound of Formula 1 may be synthesized
using a suitable organic synthesis method. A synthesis method of
the organometallic compound of Formula 1 will be understood by
those skilled in the art from the examples that will be described
below.
[0140] The organometallic compound of Formula 1 may be used between
a pair of electrodes of an organic light-emitting device, for
example, in an emission layer of the organic light-emitting
device.
[0141] According to an embodiment, an organic light-emitting device
may include a first electrode, a second electrode disposed opposite
to the first electrode, and an organic layer disposed between the
first electrode and the second electrode, wherein the organic layer
may include at least one of the organometallic compounds of Formula
1 described above.
[0142] As used herein, phrases like, for example, "the organic
layer includes at least one organometallic compound" mean that "the
organic layer includes one of the organometallic compounds of
Formula 1 above, or at least two different organometallic compounds
of Formula 1 above."
[0143] The organic layer may include at least one layer selected
from among a hole injection layer, a hole transport layer, a
functional layer having both hole injection and hole transport
capabilities (hereinafter, "H-functional layer"), a buffer layer,
an electron blocking layer, an emission layer, a hole blocking
layer, an electron transport layer, an electron injection layer,
and a functional layer having both electron injection and electron
transport capabilities (hereinafter, "E-functional layer").
[0144] The term "organic layer" as used herein may refer to a
single layer and/or a plurality of layers disposed between the
first and second electrodes of the organic light-emitting
device.
[0145] The organic layer may include an emission layer, and the
emission layer may include the organometallic compound of Formula 1
described above. The emission layer including the organometallic
compound may emit light generated based on the mechanism of
phosphorescence.
[0146] In an embodiment, the organometallic compound in the
emission layer of the organic light-emitting device may serve as a
dopant, and the emission layer may further include a
carbazole-based compound as a host.
[0147] An example of the carbazole-based compound available as a
host is a compound represented by Formula 10 below:
##STR00069##
[0148] In Formula 10, Ar.sub.1 may be a substituted or
unsubstituted C.sub.1-C.sub.60alkylene group, a substituted or
unsubstituted C.sub.2-C.sub.60 alkenylene group, --N(R.sub.100)--
(where R.sub.100 may be a substituted or unsubstituted
C.sub.6-C.sub.60aryl group, or a substituted or unsubstituted
C.sub.2-C.sub.60 heteroaryl group), a substituted or unsubstituted
C.sub.6-C.sub.60 arylene group, or a substituted or unsubstituted
C.sub.2-C.sub.60heteroarylene group; p may be an integer from 0 to
10; R.sub.91 to R.sub.96 each independently may be a hydrogen atom,
a deuterium atom, a halogen atom, a hydroxyl group, a cyano group,
a nitro group, an amino group, an amidino group, a hydrazine, a
hydrazone, a carboxyl group or a salt thereof, a sulfonic acid
group or a salt thereof, a phosphoric acid group or a salt thereof,
a substituted or unsubstituted C.sub.1-C.sub.60 alkyl group, a
substituted or unsubstituted C.sub.2-C.sub.60 alkenyl group, a
substituted or unsubstituted C.sub.2-C.sub.60 alkynyl group, a
substituted or unsubstituted C.sub.1-C.sub.60 alkoxy group, a
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 cycloalkenyl group, a
substituted or unsubstituted C.sub.3-C.sub.10 heterocycloalkyl
group, a substituted or unsubstituted C.sub.3-C.sub.10
heterocycloalkenyl group, a substituted or unsubstituted
C.sub.6-C.sub.60 aryl group, a substituted or unsubstituted
C.sub.6-C.sub.60 aryloxy group, a substituted or unsubstituted
C.sub.6-C.sub.60 arylthio group, or a substituted or unsubstituted
C.sub.2-C.sub.60 heteroaryl group, wherein adjacent two
substituents of R.sub.91 to R.sub.96 are optionally linked together
to form a substituted or unsubstituted C.sub.4-C.sub.20 alicyclic
group, a substituted or unsubstituted C.sub.2-C.sub.20
heteroalicyclic group, a substituted or unsubstituted
C.sub.6-C.sub.20 aromatic ring, or a substituted or unsubstituted
C.sub.2-C.sub.20 heteroaromatic ring; and q, r, s, t, u, and v each
independently may be an integer from 1 to 4.
[0149] In Formula 10, Ar.sub.1 may be a C.sub.1-C.sub.5 alkylene
group, a C.sub.2-C.sub.5 alkenylene group, --C(.dbd.O)--, or
--N(R.sub.100)--, wherein R.sub.100 may be at least one of a phenyl
group, a naphthyl group, an anthryl group, a fluorenyl group, a
carbazolyl group, a pyridinyl group, a pyrimidinyl group, and a
triazinyl group; and a phenyl group, a naphthyl group, an anthryl
group, a fluorenyl group, a carbazolyl group, a pyridinyl group, a
pyrimidinyl group, and a triazinyl group that are substituted with
at least one of a deuterium atom, a halogen atom, a hydroxyl group,
a cyano group, a nitro group, an amino group, a C.sub.1-C.sub.10
alkyl group, a C.sub.1-C.sub.20 alkoxy group, a phenyl group, a
naphthyl group, an anthryl group, a fluorenyl group, a carbazolyl
group, a pyridinyl group, a pyrimidinyl group, and a triazinyl
group.
[0150] In Formula 10, R.sub.91 to R.sub.96 each independently may
be one of a hydrogen atom, a deuterium atom, a halogen atom, a
hydroxyl group, a cyano group, a nitro group, an amino group, an
amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a C.sub.1-C.sub.20 alkyl group, and a
C.sub.1-C.sub.20 alkoxy group; and a C.sub.1-C.sub.20 alkyl group
and a C.sub.1-C.sub.20 alkoxy group that are substituted with at
least one of a deuterium atom, a halogen atom, a hydroxyl group, a
cyano group, a nitro group, and an amino group.
[0151] The carbazole-based compound may be, e.g., one of the
following compounds H1-H30:
##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074##
##STR00075## ##STR00076## ##STR00077##
[0152] FIG. 1 illustrates a schematic sectional view of an organic
light-emitting according to an embodiment. Hereinafter, a structure
of an organic light-emitting device according to an embodiment and
a method of manufacturing the same will be described with reference
to FIG. 1.
[0153] The substrate 11 may be a suitable substrate for use in an
organic light-emitting device. In an embodiment, the substrate 11
may be a glass substrate or a transparent plastic substrate with
strong mechanical strength, thermal stability, transparency,
surface smoothness, ease of handling, and water resistance.
[0154] A first electrode 13 may be formed by depositing or
sputtering a first electrode-forming material on a surface of the
substrate 11. When the first electrode 13 is an anode, a material
having a high work function may be used as the first
electrode-forming material to facilitate hole injection. The first
electrode 13 may be a reflective electrode or a transmission
electrode. Suitable first electrode-forming materials may be
transparent and conductive materials such as ITO, IZO, SnO.sub.2,
and ZnO. The first electrode 13 may be formed as a reflective
electrode using magnesium (Mg), aluminum (Al), aluminum-lithium
(Al--Li), calcium (Ca), magnesium-indium (Mg--In), magnesium-silver
(Mg--Ag), or the like.
[0155] The first electrode 13 may have a single-layer structure or
a multi-layer structure including at least two layers. For example,
the first electrode 13 may have a three-layered structure of
ITO/Ag/ITO.
[0156] The organic layer 15 may be disposed on the first electrode
13.
[0157] The organic layer 15 may include a hole injection layer
(HIL), a hole transport layer (HTL), a buffer layer, an emission
layer (EML), an electron transport layer (ETL), and an electron
injection layer (EIL).
[0158] The HIL may be formed on the first electrode 13 by vacuum
deposition, spin coating, casting, Langmuir-Blodgett (LB)
deposition, or the like.
[0159] When the HIL is formed using vacuum deposition, vacuum
deposition conditions may vary according to the compound that is
used to form the HIL, and the desired structure and thermal
properties of the HIL to be formed. For example, vacuum deposition
may be performed at a temperature of about 100.degree. C. to about
500.degree. C., a pressure of about 10-8 torr to about 10-3 torr,
and a deposition rate of about 0.01 to about 100 .ANG./sec.
[0160] When the HIL is formed using spin coating, the coating
conditions may vary according to the compound that is used to form
the HIL, and the desired structure and thermal properties of the
HIL to be formed. For example, the coating rate may be in the range
of about 2000 rpm to about 5000 rpm, and a temperature at which
heat treatment may be performed to remove a solvent after coating
may be in the range of about 80.degree. C. to about 200.degree.
C.
[0161] The HIL may be formed of a suitable material for a HIL. For
example, the material that can be used to form the HIL are
N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-di-
amine, (DNTPD), a phthalocyanine compound such as copper
phthalocyanine, 4,4',4''-tris (3-methylphenylphenylamino)
triphenylamine (m-MTDATA),
N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), TDATA, 2T-NATA,
polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA),
poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)
(PEDOT/PSS), polyaniline/camphor sulfonic acid (Pani/CSA), and
polyaniline)/poly(4-styrenesulfonate (PANI/PSS).
##STR00078##
[0162] The thickness of the HIL may be about 100 .ANG. to about
10000 .ANG., and in an embodiment, may be from about 100 .ANG. to
about 1000 .ANG.. When the thickness of the HIL is within these
ranges, the HIL may have good hole injecting ability without a
substantial increase in driving voltage.
[0163] Then, a HTL may be formed on the HIL by using vacuum
deposition, spin coating, casting, Langmuir-Blodgett (LB)
deposition, or the like. When the HTL is formed using vacuum
deposition or spin coating, the conditions for deposition and
coating may be similar to those for the formation of the HIL,
though the conditions for the deposition and coating may vary
according to the material that is used to form the HTL.
[0164] Examples of suitable HTL forming materials are carbazole
derivatives, such as N-phenylcarbazole or polyvinylcarbazole,
N,N'-bis(3-methylphenyl)-N,N-diphenyl-[1,1-biphenyl]-4,4'-diamine
(TPD), 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA), and
N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine) (NPB).
##STR00079##
[0165] The thickness of the HTL may be about 50 .ANG. to about 2000
.ANG., and for example, about 100 .ANG. to about 1500 .ANG.. When
the thickness of the HTL is within these ranges, the HTL may have
good hole transporting ability without a substantial increase in
driving voltage.
[0166] The H-functional layer (having both hole injection and hole
transport capabilities) may contain at least one material from each
group of the hole injection layer materials and hole transport
layer materials. The thickness of the H-functional layer may be
from about 500 .ANG. to about 10,000 .ANG., and in an embodiment,
may be from about 100 .ANG. to about 1,000 .ANG.. When the
thickness of the H-functional layer is within these ranges, the
H-functional layer may have good hole injection and transport
capabilities without a substantial increase in driving voltage.
[0167] In an embodiment, at least one of the HIL, HTL, and
H-functional layer may include at least one of a compound of
Formula 300 below and a compound of Formula 301 below:
##STR00080##
[0168] In Formula 300, Ar.sub.101 and Ar.sub.102 each independently
may be a substituted or unsubstituted C.sub.6-C.sub.60 arylene
group. In an embodiment, Ar.sub.101 and Ar.sub.102 each
independently may be one of a phenylene group, a pentalenylene
group, an indenylene group, a naphthylene group, an azulenylene
group, a heptalenylene group, an acenaphthylene group, a
fluorenylene group, a phenalenylene group, a phenanthrenylene
group, an anthracenylene group, a fluoranthenylene group, a
triphenylenylene group, a pyrenylenylene group, a chrysenylene
group, a naphthacenylene group, a picenylene group, a perylenylene
group, and a pentacenylene group; and a phenylene group, a
pentalenylene group, an indenylene group, a naphthylene group, an
azulenylene group, a heptalenylene group, an acenaphthylene group,
a fluorenylene group, a phenalenylene group, a phenanthrenylene
group, an anthracenylene group, a fluoranthenylene group, a
triphenylenylene group, a pyrenylenylene group, a chrysenylene
group, a naphthacenylene group, a picenylene group, a perylenylene
group, and a pentacenylene group that are substituted with at least
one of a deuterium atom, a halogen atom, a hydroxyl group, a nitro
group, a cyano group, an amino group, an amidino group, hydrazine,
hydrazone, a carboxyl group or salt thereof, a sulfuric acid group
or salt thereof, a phosphoric acid group or salt thereof, a
C.sub.1-C.sub.60 alkyl group, a C.sub.2-C.sub.60 alkenyl group, a
C.sub.2-C.sub.60 alkynyl group, a C.sub.1-C.sub.60 alkoxy group, a
C.sub.3-C.sub.10 cycloalkyl group, a C.sub.3-C.sub.10 cycloalkenyl
group, a C.sub.3-C.sub.10 heterocycloalkyl group, a
C.sub.3-C.sub.10 heterocycloalkenyl group, a C.sub.6-C.sub.60 aryl
group, a C.sub.6-C.sub.60 aryloxy group, a C.sub.6-C.sub.60
arylthio group, and a C.sub.2-C.sub.60 heteroaryl group.
[0169] In Formula 300, x.sub.a and x.sub.b each independently may
be an integer from 0 to 5, for example, may be 0, 1, or 2. For
example, x.sub.a may be 1, and x.sub.b may be 0.
[0170] In Formulae 300 and 301, R.sub.101 to R.sub.108, R.sub.111
to R.sub.119, and R.sub.121 to R.sub.124 each independently may be
a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl
group, a cyano group, a nitro group, an amino group, an amidino
group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof, a substituted or unsubstituted
C.sub.1-C.sub.60 alkyl group, a substituted or unsubstituted
C.sub.2-C.sub.60 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.60 alkynyl group, a substituted or unsubstituted
C.sub.1-C.sub.60 alkoxy group, a substituted or unsubstituted
C.sub.3-C.sub.60 cycloalkyl group, a substituted or unsubstituted
C.sub.5-C.sub.60 aryl group, a substituted or unsubstituted
C.sub.5-C.sub.60 aryloxy group, or a C.sub.5-C.sub.60 arylthio
group.
[0171] In an embodiment, R.sub.101 to R.sub.108, R.sub.111 to
R.sub.119, and R.sub.121 to R.sub.124 each independently may be one
of a hydrogen atom; a deuterium atom; a halogen atom; a hydroxyl
group; a cyano group; a nitro group; an amino group; an amidino
group; a hydrazine; a hydrazone; a carboxyl group or a salt
thereof; a sulfonic acid group or a salt thereof; a phosphoric acid
group or a salt thereof; a C.sub.1-C.sub.10 alkyl group (for
example, a methyl group, an ethyl group, a propyl group, a butyl
group, a pentyl group, a hexyl group, or the like); a
C.sub.1-C.sub.10 alkoxy group (for example, a methoxy group, an
ethoxy group, a propoxy group, a butoxy group, a pentoxy group, or
the like); a C.sub.1-C.sub.10 alkyl group and a C.sub.1-C.sub.10
alkoxy group that are substituted with at least one of a deuterium
atom, a halogen atom, a hydroxyl group, a cyano group, a nitro
group, an amino group, an amidino group, a hydrazine, a hydrazone,
a carboxyl group or a salt thereof, a sulfonic acid group or a salt
thereof, and a phosphoric acid group or a salt thereof; a phenyl
group; a naphthyl group; an anthryl group; a fluorenyl group; a
pyrenyl group; and a phenyl group, a naphthyl group, an anthryl
group, a fluorenyl group, and a pyrenyl group that are substituted
with at least one of a deuterium atom, a halogen atom, a hydroxyl
group, a cyano group, a nitro group, an amino group, an amidino
group, a hydrazine, a hydrazone, a carboxyl group or a salt
thereof, a sulfonic acid group or a salt thereof, a phosphoric acid
group or a salt thereof; a C.sub.1-C.sub.10 alkyl group, and a
C.sub.1-C.sub.10 alkoxy group.
[0172] In Formula 300, R.sub.109 may be one of a phenyl group, a
naphthyl group, an anthryl group, a biphenyl group, and a pyridyl
group; and a phenyl group, a naphthyl group, an anthryl group, a
biphenyl group, and a pyridyl group that are substituted with at
least one of a deuterium atom, a halogen atom, a hydroxyl group, a
cyano group, a nitro group, an amino group, an amidino group, a
hydrazine, a hydrazone, a carboxyl group or a salt thereof, a
sulfonic acid group or a salt thereof, a phosphoric acid group or a
salt thereof, a substituted or unsubstituted C.sub.1-C.sub.20 alkyl
group, and a substituted or unsubstituted C.sub.1-C.sub.20 alkoxy
group.
[0173] In an embodiment, the compound of Formula 300 may be a
compound represented by Formula 300A below:
##STR00081##
[0174] In Formula 300A, R.sub.101, R.sub.110, R.sub.121, and
R.sub.109 may be as set forth above.
[0175] In an embodiment, at least one of the HIL, HTL, and
H-functional layer may include, e.g., at least one of compounds
represented by Formulae 301 to 320 below:
##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086##
##STR00087## ##STR00088##
[0176] At least one of the HIL, HTL, and H-functional layer may
further include a charge-generating material for improved layer
conductivity, in addition to a suitable hole injecting material,
hole transport material, and/or material having both hole injection
and hole transport capabilities as described above.
[0177] The charge-generating material may be, for example, a
p-dopant. The p-dopant may be, for example, one of quinine
derivatives, metal oxides, and compounds with a cyano group.
Examples of the p-dopant are quinone derivatives such as
tetracyanoquinonedimethane (TCNQ),
2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ),
and the like; metal oxides such as tungsten oxide, molybdenum
oxide, and the like; and cyano-containing compounds such as
Compound 200 below.
##STR00089##
[0178] When the hole injection layer, hole transport layer, or
H-functional layer further includes a charge-generating material,
the charge-generating material may be homogeneously dispersed or
unhomogeneously distributed in the layer.
[0179] A buffer layer may be disposed between at least one of the
HIL, HTL, and H-functional layer, and the EML. The buffer layer may
compensate for an optical resonance distance of light according to
a wavelength of the light emitted from the EML, and thus may
increase efficiency. The buffer layer may include a suitable hole
injecting material or hole transporting material. In some other
embodiments, the buffer layer may include the same material as one
of the materials included in the HIL, HTL, and H-functional layer
that underlie the buffer layer.
[0180] Then, an EML may be formed on the HTL, H-functional layer,
or buffer layer by vacuum deposition, spin coating, casting,
Langmuir-Blodget (LB) deposition, or the like. When the EML is
formed using vacuum deposition or spin coating, the deposition and
coating conditions may be similar to those for the formation of the
HIL, though the conditions for deposition and coating may vary
according to the material that is used to form the EML.
[0181] The EML may include the organometallic compound (as a
dopant) represented by Formula 1 above, and a host.
[0182] An amount of the dopant (i.e., the organometallic compound
of Formula 1) in the EML may be selected from a range of, e.g.,
about 0.01 to about 15 parts by weight based on 100 parts by weight
of the host.
[0183] The thickness of the EML may be from about 100 .ANG. to
about 1000 .ANG., and in an embodiment, may be from about 200 .ANG.
to about 600 .ANG.. When the thickness of the EML is within these
ranges, the EML may have good light emitting ability without a
substantial increase in driving voltage.
[0184] A hole blocking layer (HBL) may be formed on the EML to
prevent diffusion of triplet excitons or holes into the ETL. When
the HBL is formed using vacuum deposition or spin coating, the
conditions for deposition and coating may be similar to those for
the formation of the HIL, although the conditions for deposition
and coating may vary according to the material that is used to form
the HBL. A suitable hole-blocking material may be used. Examples of
hole-blocking materials are oxadiazole derivatives, triazole
derivatives, and phenanthroline derivatives. For example,
bathocuproine (BCP) represented by the following formula may be
used as a material for forming the HBL.
##STR00090##
[0185] The thickness of the HBL may be from about 200 .ANG. to
about 1000 .ANG., and in an embodiment, may be from about 30 .ANG.
to about 300 .ANG.. When the thickness of the HBL is within these
ranges, the HBL may have improved hole blocking ability without a
substantial increase in driving voltage.
[0186] Then, an ETL may be formed on the HBL by a suitable method,
for example, vacuum deposition, spin coating, or casting. When the
ETL is formed using vacuum deposition or spin coating, the
deposition and coating conditions may be similar to those for the
formation of the HIL, though the deposition and coating conditions
may vary according to a compound that is used to form the ETL. A
material for forming the ETL may be a suitable material that can
stably transport electrons injected from an electron injecting
electrode (cathode). Examples of materials for forming the ETL are
a quinoline derivative, such as tris(8-quinolinorate)aluminum
(Alq3), TAZ, BAlq, beryllium bis(benzoquinolin-10-olate) (Bebq2),
9,10-di(naphthalene-2-yl)anthracene (ADN), Compound 201, and
Compound 202.
##STR00091## ##STR00092##
[0187] The thickness of the ETL may be from about 100 .ANG. to
about 1000 .ANG., and in an embodiment, may be from about 150 .ANG.
to about 500 .ANG.. When the thickness of the ETL is within these
ranges, the ETL may have satisfactory electron transporting ability
without a substantial increase in driving voltage.
[0188] In an embodiment the ETL may further include a
metal-containing material, in addition to a suitable
electron-transporting organic compound.
[0189] The metal-containing material may include a lithium (Li)
compound. Examples of the Li compound are lithium quinolate (LiQ)
and Compound 203 below:
##STR00093##
[0190] Then, an EIL, which may facilitate injection of electrons
from the cathode, may be formed on the ETL. A suitable
electron-injecting material may be used to form the EIL.
[0191] Examples of materials for forming the EIL are LiF, NaCl,
CsF, Li.sub.2O, and BaO. The deposition and coating conditions for
forming the EIL may be similar to those for the formation of the
HIL, though the deposition and coating conditions may vary
according to the material that is used to form the EIL.
[0192] The thickness of the EIL may be from about 1 .ANG. to about
100 .ANG., and in an embodiment, may be from about 3 .ANG. to about
90 .ANG.. When the thickness of the EIL is within these ranges, the
EIL may have satisfactory electron injection ability without a
substantial increase in driving voltage.
[0193] A second electrode 17 may be disposed on the organic layer
15. The second electrode 17 may be a cathode that is an electron
injection electrode. A material for forming the second electrode 17
may be a metal, an alloy, an electro-conductive compound, which may
have a low work function, or a mixture thereof. In an embodiment,
the second electrode 17 may be a transmission (e.g., transparent)
electrode and may be formed using a thin film of Li, Mg, Al,
Al--Li, Ca, Mg--In, Mg--Ag, or the like. In an embodiment, to
manufacture a top-emission light-emitting device, the transmission
electrode may be formed of indium tin oxide (ITO) or indium zinc
oxide (IZO).
[0194] The above description of the organic light-emitting device
illustrated in FIG. 1 is given by way of example.
[0195] The following Examples and Comparative Examples are provided
in order to highlight characteristics of one or more embodiments,
but it will be understood that the Examples and Comparative
Examples are not to be construed as limiting the scope of the
embodiments, nor are the Comparative Examples to be construed as
being outside the scope of the embodiments. Further, it will be
understood that the embodiments are not limited to the particular
details described in the Examples and Comparative Examples.
[0196] Examples of the unsubstituted C.sub.1-C.sub.60 alkyl group
used herein are linear or branched C.sub.1-C.sub.60 alkyl groups,
such as methyl group, ethyl group, propyl group, isobutyl group,
sec-butyl group, pentyl group, iso-amyl group, hexyl group, or the
like. In the substituted C.sub.1-C.sub.60 alkyl group, at least one
hydrogen atom of the unsubstituted C.sub.1-C.sub.60 alkyl group
described above may be substituted with a deuterium atom, a halogen
atom, a hydroxyl group, a nitro group, a cyano group, an amino
group, an amidino group, a hydrazine, a hydrazone, a carboxyl group
or salts thereof, a sulfonic acid group or salts thereof, a
phosphoric acid group or salts thereof, a C.sub.1-C.sub.60 alkyl
group, a C.sub.2-C.sub.60 alkenyl group, a C.sub.2-C.sub.60 alkynyl
group, a C.sub.6-C.sub.60 aryl group, a C.sub.2-C.sub.60 heteroaryl
group, --N(Q.sub.11)(Q.sub.12), or
--Si(Q.sub.13)(Q.sub.14)(Q.sub.15), wherein Q.sub.1 to Q.sub.15
each independently may be selected from the group of a hydrogen
atom, a C.sub.1-C.sub.60 alkyl group, a C.sub.2-C.sub.60 alkenyl
group, a C.sub.2-C.sub.60 alkynyl group, a C.sub.5-C.sub.60 aryl
group, and a C.sub.2-C.sub.60 heteroaryl group. The unsubstituted
C.sub.1-C.sub.60 alkoxy group may be a group represented by --OA,
wherein A is an unsubstituted C.sub.1-C.sub.60 alkyl group
described above.
[0197] Examples of the unsubstituted C.sub.1-C.sub.60 alkoxy group
are a methoxy group, an ethoxy group, and an isopropyloxy group. At
least one of the hydrogen atoms in the alkoxy group may be
substituted with the substituents described above in conjunction
with the substituted C.sub.1-C.sub.60 alkyl group.
[0198] As used herein, the unsubstituted C.sub.2-C.sub.60 alkenyl
group may be a hydrocarbon chain having a carbon-carbon double bond
in the center or at a terminal of the unsubstituted
C.sub.2-C.sub.60 alkyl group. Examples of the unsubstituted
C.sub.2-C.sub.60 alkenyl group are ethenyl group, propenyl group,
and butenyl groups. At least one hydrogen atom in the unsubstituted
C.sub.2-C.sub.60 alkenyl group may be substituted with the
substituents described in conjunction with the substituted
C.sub.1-C.sub.60 alkyl group.
[0199] The unsubstituted C.sub.2-C.sub.60 alkynyl group may be a
hydrocarbon chain having at least one carbon-carbon triple bond in
the center or at a terminal thereof. Examples of the unsubstituted
C.sub.2-C.sub.60 alkynyl group are an ethenyl group, a propenyl
group, a butenyl group, and the like. At least one hydrogen atom in
the alkynyl group may be substituted with the substituents
described above in conjunction with the C.sub.1-C.sub.60 alkyl
group.
[0200] The unsubstituted C.sub.6-C.sub.60 aryl group may be a
monovalent group having a carbocyclic aromatic system having 6 to
60 carbon atoms including at least one aromatic ring. The
unsubstituted C.sub.6-C.sub.60 arylene group may be a bivalent
group having a carbocyclic aromatic system having 6 to 60 carbon
atoms including at least one aromatic ring. When the aryl group and
the arylene group have at least two rings, they may be fused to
each other via a single bond. At least one hydrogen atom in the
aryl group and the arylene group may be substituted with the
substituents described above in conjunction with the
C.sub.1-C.sub.60 alkyl group.
[0201] Examples of the substituted or unsubstituted
C.sub.6-C.sub.60 aryl group are a phenyl group, a C.sub.1-C.sub.10
alkylphenyl group (e.g., an ethylphenyl group), a C.sub.1-C.sub.10
alkylbiphenyl group (e.g., an ethylbiphenyl group), a halophenyl
group (e.g., an o-, m-, or p-fluorophenyl group and a
dichlorophenyl group), a dicyanophenyl group, a
trifluoromethoxyphenyl group, an o-, m-, or p-tolyl group, an o-,
m- or p-cumenyl group, a mesityl group, a phenoxyphenyl group, a
(.alpha.,.alpha.-dimethylbenzene)phenyl group, a
(N,N'-dimethyl)aminophenyl group, a (N,N'-diphenyl)aminophenyl
group, a pentalenyl group, an indenyl group, a naphthyl group, a
halonaphthyl group (e.g., a fluoronaphthyl group), a
C.sub.1-C.sub.10 alkylnaphthyl group (e.g., a methylnaphthyl
group), a C.sub.1-C.sub.10 alkoxynaphthyl group (e.g., a
methoxynaphthyl group), an anthracenyl group, an azulenyl group, a
heptalenyl group, an acenaphthylenyl group, a phenalenyl group, a
fluorenyl group, an anthraquinolyl group, a methylanthryl group, a
phenanthryl group, a triphenylenyl group, a pyrenyl group, a
chrysenyl group, an ethyl-chrysenyl group, a picenyl group, a
perylenyl group, a chloroperylenyl group, a pentaphenyl group, a
pentacenyl group, a tetraphenylenyl group, a hexaphenyl group,
hexacenyl group, a rubicenyl group, a coronenyl group, a
trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a
pyranthrenyl group, and an ovalenyl group. Examples of the
substituted C.sub.5-C.sub.60 aryl group may be inferred based on
those of the unsubstituted C.sub.5-C.sub.60 aryl group and the
substituted C.sub.1-C.sub.60 alkyl group described above. Examples
of the substituted or unsubstituted C.sub.5-C.sub.60 arylene group
may be inferred based on those examples of the substituted or
unsubstituted C.sub.5-C.sub.60 aryl group described above.
[0202] The unsubstituted C.sub.2-C.sub.60 heteroaryl group may be a
monovalent group having at least one aromatic ring having at least
one of the heteroatoms selected from the group of N, O, P, and S.
The unsubstituted C.sub.2-C.sub.60 heteroarylene group may be a
divalent group having at least one aromatic ring having at least
one of the heteroatoms selected from the group of N, O, P, and S.
In this regard, when the heteroaryl group and the heteroarylene
group have at least two rings, they may be fused to each other via
a single bond. At least one hydrogen atom in the heteroaryl group
and the heteroarylene group may be substituted with those
substituents described above in conjunction with the
C.sub.1-C.sub.60 alkyl group.
[0203] Examples of the unsubstituted C.sub.2-C.sub.60 heteroaryl
group are a pyrazolyl group, an imidazolyl group, an oxazolyl
group, a thiazolyl group, a triazolyl group, a tetrazolyl group, an
oxadiazolyl group, a pyridinyl group, a pyridazinyl group, a
pyrimidinyl group, a triazinyl group, a carbazolyl group, an
indolyl group, a quinolinyl group, an isoquinolinyl group, a
benzoimidazolyl group, an imidazopyridinyl group and an
imidazopyrimidinyl group. Examples of the substituted
C.sub.2-C.sub.60 heteroarylene group may be inferred based on those
examples of the substituted or unsubstituted C.sub.2-C.sub.60
arylene group described above.
[0204] The substituted or unsubstituted C.sub.6-C.sub.60 aryloxy
group may be --OA.sub.2 (wherein A.sub.2 may be a substituted or
unsubstituted C.sub.6-C.sub.60 aryl group described above). The
substituted or unsubstituted C.sub.5-C.sub.60 arylthio group may be
--SA.sub.3 (wherein A.sub.3 may be a substituted or unsubstituted
C.sub.6-C.sub.60 aryl group described above).
Synthesis Examples
[0205] Ligand 1 (L1) to ligand 43 (L43)
##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098##
##STR00099## ##STR00100## ##STR00101## ##STR00102##
[0206] Ligand Synthesis 1: Synthesis of ligand 1 L1)
[0207] Ligand 1 (L1) was synthesized according to Reaction Scheme 1
below:
##STR00103##
[0208] Synthesis of Intermediate 1(3)
[0209] Following adding 1.9 g (80.8 mmol) of NaH to 80 ml of
dichlormethane, 5.0 g (73.5 mmol) of pyrazole was added thereto at
0.degree. C. and then stirred for about 30 minutes. Afterward, 11.5
ml (80.8 mmol) of benzyl chloroformate dissolved in 30 ml of
dichloromethane was dropwise added thereto at 0.degree. C., and
stirred for about 1 hour, then further at room temperature for
about 3 hours. After completion of the reaction, 100 ml of
saturated sodium hydrocarbonate was added thereto, followed by
extraction with 50 ml of methylene chloride three times to obtain
an organic layer, which was then dried using magnesium sulfate,
followed by distillation under reduced pressure. The resulting
product was separated and purified using column chromatography to
obtain 12.6 g (62.4 mmol, Yield: 85%) of Intermediate 1(3). This
compound was identified using liquid chromatography-mass
spectroscopy (LC-MS).
[0210] LC-MS m/z=203 (M+H)+
[0211] Synthesis of Intermediate 1(2)
[0212] After dissolving 10.0 g (49.5 mmol) of Intermediate 1(3) in
80 ml of anhydrous tetrahydrofuran, 25 ml (2.2M in THF, 54.5 mmol)
of n-BuLi was slowly added thereto at 0.degree. C., and stirred at
room temperature for about 1 hour. After 1 hour, the temperature
was lowered to about -78.degree. C., 12.0 ml (59.4 mmol) of
isopropyl pinacol borate was slowly added to the reaction mixture,
and stirred at -78.degree. C. for about 15 minutes. Afterward, the
temperature was slowly increased to 0.degree. C., and the reaction
mixture was further stirred for about 1 hour. After completion of
the reaction, 100 ml of a saturated chloroammonium solution as
added thereto, and extracted with 100 ml of dichloromethane to
obtain an organic layer, which was then washed with 100 mL of
distilled water twice and dried using magnesium sulfate, followed
by distillation under reduced pressure to obtain 9.7 g (29.7 mmol,
Yield: 60%) of Intermediate 1(2).
[0213] LC-MS m/z=329(M+H)+
[0214] Synthesis of Intermediate 1(1)
[0215] After dissolving 1.9 g (12.2 mmol) of 4-bromopyrimidine in
120 ml of a mixed solvent of dioxolane and water (5:1) in a
seal-tube, 5.0 g (36.6 mmol) of potassium carbonate, 1.4 g (1.2
mmol) of Tetrakistriphenylphosphine Pd(0), and 8.0 g (24.4 mmol) of
Intermediate 1(2) were added thereto. The resulting reaction
mixture was stirred at 90.degree. C. for a day. After completion of
the reaction, 100 ml of distilled water was added to the reaction
product, followed by extraction with 100 ml of dichloromethane to
obtain an organic layer, which was then dried using magnesium
sulfate, and distilled under reduced pressure to obtain 2.0 g (7.3
mmol, Yield: 60%) of Intermediate 1(1).
[0216] LC-MS m/z=280(M+H)+
[0217] Synthesis of Ligand 1 (L1)
[0218] After dissolving 2.0 g (7.3 mmol) of Intermediate 1(1) in 60
ml of methanol at room temperature, 0.2 g of Pd/C (10% w/w) was
added thereto and stirred at room temperature for about 12 hours
with hydrogen purging After completion of the reaction, Pd/C was
removed using CELITE to obtain an organic layer, which was then
concentrated under reduced pressure. The resulting product was
separated and purified using column chromatography to obtain 1.0 g
(6.9 mmol, Yield: 95%) of ligand 1 (L1). This compound was
identified using LC-MS.
[0219] LC-MS m/z=203(M+14)+
[0220] Ligand Synthesis 2: Synthesis of Ligand 2 (L2)
[0221] Ligand 2 (L2) was synthesized according to Reaction Scheme 2
below:
##STR00104##
[0222] Synthesis of Ligand 2 (L2)
[0223] After dissolving 2.0 g (12.6 mmol) of 4-bromopyrimidine in
80 ml of 1,2-dimethoxyethane at room temperature, 1.4 g (1.2 mmol)
of tetrakistriphenylphosphine Pd(0), and 4.6 g (18.9 mmol) of
1H-indazol-3-ylboronic acid pinacol ester were added thereto. The
resulting reaction mixture was heated at about 90.degree. C. for
about 18 hours under reflux. After completion of the reaction, 100
ml of distilled water was added to the reaction product, followed
by extraction with 100 ml of dichloromethane to obtain an organic
layer, which was then dried using magnesium sulfate, distilled
under reduced pressure, and then separated and purified using
column chromatography to obtain 1.1 g (5.7 mmol, Yield: 45%) of
ligand 2 (L2).
[0224] LC-MS m/z=197(M+H)+
[0225] Ligand Synthesis 3: Synthesis of Ligand 3 (L3)
[0226] Ligand 3 (L3) was synthesized according to Reaction Scheme 3
below:
##STR00105##
[0227] 0.8 g (3.2 mmol, Yield: 25%) of ligand 3 (L3) was
synthesized in the same manner as in the synthesis of ligand 2 (L2)
(Ligand Synthesis 2), except that 4-bromoquinazoline, instead of
4-bromopyrimidine, was used in synthesizing Ligand (L3).
[0228] LC-MS m/z=197(M+H)+
[0229] Ligand Synthesis 4: Synthesis of Ligand 4 (L4)
[0230] Ligand 4 (L4) was synthesized according to Reaction Scheme 4
below:
##STR00106##
[0231] Synthesis of Intermediate 4(1)
[0232] Following adding 1.0 g (43.4 mmol) of NaH to 80 ml of
anhydrous tetrahydrofuran, 2.6 ml (34.8 mmol) of acetone was slowly
added thereto at 0.degree. C. After 1 hour, 4.0 g (29.0 mmol) of
pyrimidine-4-carboxylic acid methyl ester was slowly added thereto
and heated under reflux at about 80.degree. C. for about 16 hours.
After completion of the reaction, 30 ml of distilled water was
added thereto, 2.5 ml of acetic was then slowly added and stirred
at room temperature for about 30 minutes. After 30 minutes, the
resulting product was extracted with 100 ml of dichloromethane five
times to obtain an organic layer, which was dried using magnesium
sulfate and distilled under reduced pressure. The resulting product
was separated and purified using column chromatography to obtain
1.8 g (11.0 mmol, Yield 38%) of Intermediate 4(1).
[0233] LC-MS m/z=165(M+H)+
[0234] Synthesis of Ligand 4 (L4)
[0235] After dissolving 1.8 g (11.0 mmol) of Intermediate 4(1) in
30 ml of ethanol at room temperature, 1.6 ml (55.0 mmol) of
hydrazine hydrate was added thereto and heated under reflux at
about 80.degree. C. for about 18 hours. After completion of the
reaction, the reaction product was concentrated under reduced
pressure and extracted with 80 ml of distilled water and 100 ml of
dichloromethane to obtain an organic layer, which was then dried
using magnesium sulfate, distilled under reduced pressure, and then
separated and purified using column chromatography to obtain 1.5 g
(9.3 mmol, Yield: 88%) of ligand 4 (L4).
[0236] LC-MS m/z=161(M+H)+
[0237] Ligand Synthesis 5: Synthesis of Ligand 5 (L5)
[0238] Ligand 5 (L5) was synthesized according to Reaction Scheme 5
below:
##STR00107##
[0239] Ligand 5 (L5) was synthesized in the same manner (Yield:
25%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that 3,3-methylbutane-2-one, instead of acetone, was used in
synthesizing Intermediate 4(1).
[0240] LC-MS m/z=189(M+H)+
[0241] Ligand Synthesis 6: Synthesis of Ligand 6 (L6)
[0242] Ligand 6 (L6) was synthesized according to Reaction Scheme 6
below:
##STR00108##
[0243] Ligand 6 (L6) was synthesized in the same manner (Yield:
21%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that 3,3-dimethylbutane-2-one, instead of acetone, was used
in synthesizing Intermediate 4(1).
[0244] LC-MS m/z=203(M+H)+
[0245] Ligand Synthesis 7: Synthesis of Ligand 7 (L7)
[0246] Ligand 7 (L7) was synthesized according to Reaction Scheme 7
below:
##STR00109##
[0247] Ligand 7 (L7) was synthesized in the same manner (Yield:
63%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that 1,1,1-trifluoropropan-2-one, instead of acetone, was
used in synthesizing Intermediate 4(1).
[0248] LC-MS m/z=215(M+H)+
[0249] Ligand Synthesis 8: Synthesis of Ligand 8 (L8)
[0250] Ligand 8 (L8) was synthesized according to Reaction Scheme 8
below:
##STR00110##
[0251] Ligand 8 (L8) was synthesized in the same manner (Yield:
35%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that cyclohexanone, instead of acetone, was used in
synthesizing Intermediate 4(1).
[0252] LC-MS m/z=201(M+H)+
[0253] Ligand Synthesis 9: Synthesis of Ligand 9 (L9)
[0254] Ligand 9 (L9) was synthesized according to Reaction Scheme 9
below:
##STR00111##
[0255] Ligand 9 (L9) was synthesized in the same manner (Yield:
43%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that 2,2-dimethylcyclohexanone, instead of acetone, was used
in synthesizing Intermediate 4(1).
[0256] LC-MS m/z=229(M+H)+
[0257] Ligand Synthesis 10: Synthesis of Ligand 10 (L10)
[0258] Ligand 10 (L10) was synthesized according to Reaction Scheme
10 below:
##STR00112##
[0259] Ligand 10 (L10) was synthesized in the same manner (Yield:
65%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that camper, instead of acetone, was used in synthesizing
Intermediate 4(1).
[0260] LC-MS m/z=254(M+H)+
[0261] Ligand Synthesis 11: Synthesis of Ligand 11 (L11)
[0262] Ligand 11 (L11) was synthesized according to Reaction Scheme
11 below:
##STR00113##
[0263] Ligand 11 (L11) was synthesized in the same manner (Yield:
17%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that methyl 6-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 4(1).
[0264] LC-MS m/z=175(M+H)+
[0265] Ligand Synthesis 12: Synthesis of Ligand 12 (L12)
[0266] Ligand 12 (L12) was synthesized according to Reaction Scheme
12 below:
##STR00114##
[0267] Ligand 12 (L12) was synthesized in the same manner (Yield:
12%) as in the synthesis of ligand 6 (L6) (Ligand Synthesis 6),
except that methyl 6-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 6(1).
[0268] LC-MS m/z=217(M+H)+
[0269] Ligand Synthesis 13: Synthesis of Ligand 13 (L13)
[0270] Ligand 13 (L13) was synthesized according to Reaction Scheme
13 below:
##STR00115##
[0271] Ligand 13 (L13) was synthesized in the same manner (Yield:
35%) as in the synthesis of ligand 7 (L7) (Ligand Synthesis 7),
except that methyl 6-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 7(1).
[0272] LC-MS m/z=229(M+H)+
[0273] Ligand Synthesis 14: Synthesis of Ligand 14 (L14)
[0274] Ligand 14 (L14) was synthesized according to Reaction Scheme
14 below:
##STR00116##
[0275] Ligand 14 (L14) was synthesized in the same manner (Yield:
26%) as in the synthesis of ligand 9 (L9) (Ligand Synthesis 9),
except that methyl 6-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 9(1).
[0276] LC-MS m/z=243(M+H)+
[0277] Ligand Synthesis 15: Synthesis of Ligand 15 (L15)
[0278] Ligand 15 (L15) was synthesized according to Reaction Scheme
15 below:
##STR00117##
[0279] Ligand 15 (L15) was synthesized in the same manner (Yield:
35%) as in the synthesis of ligand 10 (L10) (Ligand Synthesis 10),
except that methyl 6-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 10(1).
[0280] LC-MS m/z=269(M+H)+
[0281] Ligand Synthesis 16: Synthesis of Ligand 16 (L16)
[0282] Ligand 16 (L16) was synthesized according to Reaction Scheme
16 below:
##STR00118##
[0283] Ligand 16 (L16) was synthesized in the same manner (Yield:
14%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that methyl 6-methoxypyrimidine-4-carboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 4(1).
[0284] LC-MS m/z=191(M+H)+
[0285] Ligand Synthesis 17: Synthesis of Ligand 17 (L17)
[0286] Ligand 17 (L17) was synthesized according to Reaction Scheme
17 below:
##STR00119##
[0287] Ligand 17 (L17) was synthesized in the same manner (Yield:
12%) as in the synthesis of ligand 6 (L6) (Ligand Synthesis 6),
except that methyl 6-methoxypyrimidine-4-carboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 6(1).
[0288] LC-MS m/z=233(M+H)+
[0289] Ligand Synthesis 18: Synthesis of Ligand 18 (L18)
[0290] Ligand 18 (L18) was synthesized according to Reaction Scheme
18 below:
##STR00120##
[0291] Ligand 18 (L18) was synthesized in the same manner (Yield:
25%) as in the synthesis of ligand 7 (L7) (Ligand Synthesis 7),
except that methyl 6-methoxypyrimidine-4-carboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 7(1).
[0292] LC-MS m/z=245(M+H)+
[0293] Ligand Synthesis 19: Synthesis of Ligand 19 (L19)
[0294] Ligand 19 (L19) was synthesized according to Reaction Scheme
19 below:
##STR00121##
[0295] Ligand 19 (L19) was synthesized in the same manner (Yield:
22%) as in the synthesis of ligand 9 (L9) (Ligand Synthesis 9),
except that methyl 6-methoxypyrimidine-4-carboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 9(1).
[0296] LC-MS m/z=259(M+H)+
[0297] Ligand Synthesis 20: Synthesis of Ligand 20 (L20)
[0298] Ligand 20 (L20) was synthesized according to Reaction Scheme
20 below:
##STR00122##
[0299] Ligand 20 (L20) was synthesized in the same manner (Yield:
30%) as in the synthesis of ligand 10 (L10) (Ligand Synthesis 10),
except that methyl 6-methoxypyrimidine-4-carboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 10(1).
[0300] LC-MS m/z=285(M+H)+
[0301] Ligand Synthesis 21: Synthesis of Ligand 21 (L21)
[0302] Ligand 21 (L21) was synthesized according to Reaction Scheme
21 below:
##STR00123##
[0303] Ligand 21 (L21) was synthesized in the same manner (Yield:
26%) as in the synthesis of ligand 4 (L4) (Ligand Synthesis 4),
except that methyl 6-(trifluoromethyl)pyrimidine-4-carboxylate,
instead of pyrimidine-4-carboxylic acid methyl ester, was used in
synthesizing Intermediate 4(1).
[0304] LC-MS m/z=229(M+H)+
[0305] Ligand Synthesis 22: Synthesis of Ligand 22 (L22)
[0306] Ligand 22 (L22) was synthesized according to Reaction Scheme
22 below:
##STR00124##
[0307] Ligand 22 (L22) was synthesized in the same manner (Yield:
24%) as in the synthesis of ligand 6 (L6) (Ligand Synthesis 6),
except that methyl 6-(trifluoromethyl)pyrimidine-4-carboxylate,
instead of pyrimidine-4-carboxylic acid methyl ester, was used in
synthesizing Intermediate 6(1).
[0308] LC-MS m/z=271(M+H)+
[0309] Ligand Synthesis 23: Synthesis of Ligand 23 (L23)
[0310] Ligand 23 (L23) was synthesized according to Reaction Scheme
23 below:
##STR00125##
[0311] Ligand 23 (L23) was synthesized in the same manner (Yield:
37%) as in the synthesis of ligand 7 (L7) (Ligand Synthesis 7),
except that methyl 6-(trifluoromethyl)pyrimidine-4-carboxylate,
instead of pyrimidine-4-carboxylic acid methyl ester, was used in
synthesizing Intermediate 7(1).
[0312] LC-MS m/z=283(M+H)+
[0313] Ligand Synthesis 24: Synthesis of Ligand 24 (L24)
[0314] Ligand 24 (L24) was synthesized according to Reaction Scheme
24 below:
##STR00126##
[0315] Ligand 24 (L24) was synthesized in the same manner (Yield:
42%) as in the synthesis of ligand 10 (L10) (Ligand Synthesis 10),
except that methyl 6-(trifluoromethyl)pyrimidine-4-carboxylate,
instead of pyrimidine-4-carboxylic acid methyl ester, was used in
synthesizing Intermediate 10(1).
[0316] LC-MS m/z=323(M+H)+
[0317] Ligand Synthesis 25: Synthesis of Ligand 25 (L25)
[0318] Ligand 25 (L25) was synthesized according to Reaction Scheme
25 below:
##STR00127##
[0319] Ligand 25 (L25) was synthesized in the same manner (Yield:
17%) as in the synthesis of ligand 6 (L6) (Ligand Synthesis 6),
except that methyl 2-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 6(1).
[0320] LC-MS m/z=217(M+H)+
[0321] Ligand Synthesis 26: Synthesis of Ligand 26 (L26)
[0322] Ligand 26 (L26) was synthesized according to Reaction Scheme
26 below:
##STR00128##
[0323] Ligand 26 (L26) was synthesized in the same manner (Yield:
22%) as in the synthesis of ligand 7 (L7) (Ligand Synthesis 7),
except that methyl 2-methylpyrimidine-4-caboxylate, instead of
pyrimidine-4-carboxylic acid methyl ester, was used in synthesizing
Intermediate 7(1).
[0324] LC-MS m/z=229(M+H)+
[0325] Ligand Synthesis 27: Synthesis of Ligand 27 (L27)
[0326] Ligand 27 (L27) was synthesized according to Reaction Scheme
27 below:
##STR00129##
[0327] Synthesis of Intermediate 27(1)
[0328] Following Adding 1.9 g (19.3 Mmol) of NatOBu (Sodium
t-Butoxide) to 50 ml of anhydrous tetrahydrofuran, 2.2 g (17.5
mmol) of 2,2-dimethyl-3-pentanone was slowly added thereto at
0.degree. C. After heating the mixture at about 60.degree. C. for
about 2 hours, 2.2 g (15.7 mmol) of pyrimidine-4-carboxylic acid
methyl ester was slowly added thereto and heated under reflux at
about 80.degree. C. for about 12 hours. After completion of the
reaction, 50 ml of distilled water was added, and a 4N diluted
hydrochloric acid was added for neutralization, followed by
extraction with 100 ml of dichloromethane about three times to
obtain an organic layer, which was then dried using magnesium
sulfate, distilled under reduced pressure, and then separated and
purified using column chromatography to obtain 0.6 g (2.5 mmol,
Yield: 16%) of Intermediate 27(1).
[0329] LC-MS m/z=223(M+H)+
[0330] Synthesis of Ligand 27 (L17)
[0331] After dissolving 0.5 g (2.5 mmol) of Intermediate 27(1) in
10 ml of ethanol at room temperature, 0.7 ml (55.0 mmol) of
hydrazine hydrate was added thereto and heated under reflux at
about 80.degree. C. for about 18 hours. After completion of the
reaction, the reaction product was concentrated under reduced
pressure and extracted with 30 ml of distilled water and 50 ml of
dichloromethane to obtain an organic layer, which was then dried
using magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain 0.4 g (2.1 mmol, Yield: 85%) of ligand 27
(L27).
[0332] LC-MS m/z=217(M+H)+
[0333] Ligand Synthesis 28: Synthesis of Ligand 28 (L28)
[0334] Ligand 28 (L28) was synthesized according to Reaction Scheme
28 below:
##STR00130##
[0335] Ligand 28 (L28) was synthesized in the same manner (Yield:
12%) as in the synthesis of ligand 27 (L27) (Ligand Synthesis 27),
except that 2,2,5,5-tetramethylhexan-3-one, instead of
2,2-dimethyl-3-pentanone, was used in synthesizing Intermediate
27(1).
[0336] LC-MS m/z=259(M+H)+
[0337] Ligand Synthesis 29: Synthesis of Ligand 29 (L29)
[0338] Ligand 29 (L29) was synthesized according to Reaction Scheme
29 below:
##STR00131##
[0339] Ligand 29 (L29) was synthesized in the same manner (Yield:
9%) as in the synthesis of ligand 27 (L27) (Ligand Synthesis 27),
except that 2,2-dimethyl-4-(trifluoromethyl)-butanone, instead of
2,2-dimethyl-3-pentanone, was used in synthesizing Intermediate
27(1).
[0340] LC-MS m/z=271(M+H)+
[0341] Ligand Synthesis 30: Synthesis of Ligand 30 (L30)
[0342] Ligand 30 (L30) was synthesized according to Reaction Scheme
30 below:
##STR00132##
[0343] Ligand 30 (L30) was synthesized in the same manner (Yield:
10%) as in the synthesis of ligand 27 (L27) (Ligand Synthesis 27),
except that 1,4,-di(trifluoromethyl)-2-butanone, instead of
2,2,-dimethyl-3-pentanone, was used in synthesizing Intermediate
27(1).
[0344] LC-MS m/z=283(M+H)+
[0345] Ligand Synthesis 31: Synthesis of Ligand 31 (L31)
[0346] Ligand 31 (L31) was synthesized according to Reaction Scheme
31 below:
##STR00133##
[0347] Synthesis of Intermediate 31(2)
[0348] Following dissolving 25.0 g (143.6 mmol) of
4-quinazoline-carboxylic acid in 100 ml of methanol, 5 ml of
sulfuric acid (conc.) was added thereto, and heated under reflux at
about 80.degree. C. for about 18 hours. After completion of the
reaction, the reaction mixture was concentrated under reduced
pressure, and then dissolved in 100 ml of dichloromethane. A
saturated sodium hydrocarbonate solution was slowly added thereto
at 0.degree. C. for basification, followed by extraction to obtain
an organic layer, which was then dried using magnesium sulfate, and
distilled under reduced pressure to obtain 26.0 g (137.8 mmol,
Yield: 96%) of Intermediate 31(2).
[0349] LC-MS m/z=189(M+H)+
[0350] Synthesis of Intermediate 31(1)
[0351] Following adding 1.0 g (43.4 mmol) of NaH to 80 ml of
anhydrous tetrahydrofuran, 2.6 ml (34.8 mmol) of acetone was slowly
added thereto at 0.degree. C. After 1 hour, 5.5 g (29.0 mmol) of
Intermediate 31(2) was slowly added thereto and heated under reflux
at about 80.degree. C. for about 16 hours. After completion of the
reaction, 30 ml of distilled water was added, and a 4N diluted
hydrochloric acid solution was slowly added thereto for
neutralization. The resulting neutralized reaction mixture was
extracted with 100 ml of dichloromethane about five times to obtain
an organic layer, which was dried using magnesium sulfate and
distilled under reduced pressure. The resulting product was
separated and purified using column chromatography to obtain 3.3 g
(15.1 mmol, Yield 52%) of Intermediate 31(1).
[0352] LC-MS m/z=215(M+H)+
[0353] Synthesis of Ligand 31 (L31)
[0354] After dissolving 3.0 g (13.9 mmol) of Intermediate 31(1) in
50 ml of ethanol at room temperature, 4.0 ml (140.0 mmol) of
hydrazine hydrate was added thereto and heated under reflux at
about 80.degree. C. for about 18 hours. After completion of the
reaction, the reaction product was concentrated under reduced
pressure and extracted with 80 ml of distilled water and 100 ml of
dichloromethane to obtain an organic layer, which was then dried
using magnesium sulfate, distilled under reduced pressure, and then
separated and purified using column chromatography to obtain 2.2 g
(10.4 mmol, Yield: 75%) of ligand 31 (L31).
[0355] LC-MS m/z=211(M+H)+
[0356] Ligand Synthesis 32: Synthesis of Ligand 32 (L32)
[0357] Ligand 32 (L32) was synthesized according to Reaction Scheme
32 below:
##STR00134##
[0358] Ligand 32 (L32) was synthesized in the same manner (Yield:
25%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that 3,3-dimethylbutane-2-one, instead of acetone, was used
in synthesizing Intermediate 31(1).
[0359] LC-MS m/z=253(M+H)+
[0360] Ligand Synthesis 33: Synthesis of Ligand 33 (L33)
[0361] Ligand 33 (L33) was synthesized according to Reaction Scheme
33 below:
##STR00135##
[0362] Ligand 33 (L33) was synthesized in the same manner (Yield:
22%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that 1,1,1-trifluoropropan-2-one, instead of acetone, was
used in synthesizing Intermediate 31(1).
[0363] LC-MS m/z=265(M+H)+
[0364] Ligand Synthesis 34: Synthesis of Ligand 34 (L31)
[0365] Ligand 34 (L34) was synthesized according to Reaction Scheme
34 below:
##STR00136##
[0366] Ligand 34 (L34) was synthesized in the same manner (Yield:
20%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that cyclohexanone, instead of acetone, was used in
synthesizing Intermediate 31(1).
[0367] LC-MS m/z=251(M+H)+
[0368] Ligand Synthesis 35: Synthesis of Ligand 35 (L35)
[0369] Ligand 35 (L35) was synthesized according to Reaction Scheme
35 below:
##STR00137##
[0370] Ligand 35 (L35) was synthesized in the same manner (Yield:
22%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that 2,2-dimethylbutane-2-one, instead of acetone, was used
in synthesizing Intermediate 31(1).
[0371] LC-MS m/z=279(M+H)+
[0372] Ligand Synthesis 36: Synthesis of Ligand 36 (L36)
[0373] Ligand 36 (L36) was synthesized according to Reaction Scheme
36 below:
##STR00138##
[0374] Ligand 36 (L36) was synthesized in the same manner (Yield:
22%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that camphor, instead of acetone, was used in synthesizing
Intermediate 31(1).
[0375] LC-MS m/z=305(M+H)+
[0376] Ligand Synthesis 37: Synthesis of Ligand 37 (L37)
[0377] Ligand 37 (L37) was synthesized according to Reaction Scheme
37 below:
##STR00139##
[0378] Ligand 37 (L37) was synthesized in the same manner (Yield:
18%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that 2,2-dimethylbutane-3-one, instead of acetone, was used
in synthesizing Intermediate 31(1).
[0379] LC-MS m/z=267(M+H)+
[0380] Ligand Synthesis 38: Synthesis of Ligand 38 (L38)
[0381] Ligand 38 (L38) was synthesized according to Reaction Scheme
38 below:
##STR00140##
[0382] Ligand 38 (L38) was synthesized in the same manner (Yield:
20%) as in the synthesis of ligand 31 (L31) (Ligand Synthesis 31),
except that 2,2-dimethyl-4-(trifluoromethyl)butan-3-one, instead of
acetone, was used in synthesizing Intermediate 31(1).
[0383] LC-MS m/z=321(M+H)+
[0384] Ligand Synthesis 39: Synthesis of Ligand 39 (L39)
[0385] Ligand 39 (L39) was synthesized according to Reaction Scheme
39 below:
##STR00141##
[0386] Synthesis of Intermediate 39(4)
[0387] Following adding 2.1 g (86.8 mmol) of NaH to 120 ml of
anhydrous tetrahydrofuran, 8.7 ml (69.6 mmol) of
1,1,1-trifluoropropan-2-one was slowly added thereto at 0.degree.
C. After 1 hour, 12.6 g (58.0 mmol) of methyl
2-bromopyrimidine-4-carboxylate was slowly added thereto and heated
under reflux at about 80.degree. C. for about 16 hours. After
completion of the reaction, 100 ml of distilled water was added,
and a 1N diluted hydrochloric acid solution was slowly added
thereto and stirred at room temperature for about 30 minutes until
the reaction mixture was neutralized. After 30 minutes, the
resulting product was extracted with 100 ml of dichloromethane
about five times to obtain an organic layer, which was then dried
using magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain 5.3 g (18.6 mmol, Yield 32%) of
Intermediate 39(4).
[0388] LC-MS m/z=297(M+H)+
[0389] Synthesis of Intermediate 39(3)
[0390] After dissolving 3.0 g (10.4 mmol) of Intermediate 39(4) in
30 ml of ethanol at room temperature, 2.6 ml (100.0 mmol) of
hydrazine hydrate was added thereto and heated under reflux at
about 80.degree. C. for about 18 hours. After completion of the
reaction, the reaction product was concentrated under reduced
pressure, and then extracted with 80 ml of distilled water and 100
ml of dichloromethane to obtain an organic layer, which was then
dried using magnesium sulfate and distilled under reduced pressure.
The resulting product was separated and purified using column
chromatography to obtain 2.1 g (7.5 mmol, Yield 72%) of
Intermediate 39(3).
[0391] LC-MS m/z=293(M+H)+
[0392] Synthesis of Intermediate 39(2)
[0393] Following adding 0.2 g (9.0 mmol) of NaH to 120 ml of
anhydrous tetrahydrofuran, 2.1 g (7.5 mmol) of Intermediate 39(2)
was slowly added thereto at 0.degree. C. After 30 minutes, 1.5 ml
(8.3 mmol) of 2-(trimethylsilyl)ethoxymethyl chloride was slowly
added thereto and stirred at room temperature for about two days.
After completion of the reaction, the reaction product was
extracted with 100 ml of distilled water and 100 ml of
dichloromethane to obtain an organic layer, which was then dried
using magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain 2.7 g (6.6 mmol, Yield 88%) of
Intermediate 39(2).
[0394] LC-MS m/z=423(M+H)+
[0395] Synthesis of Intermediate 39(1)
[0396] Following dissolving 2.7 g (6.6 mmol) of Intermediate 39(2)
in 60 ml of toluene, 0.05 g (0.05 mmol) of
tris(dibenzylideneacetone)dipalladium(0), 0.2 ml (2.6 mmol) of
aniline, 0.06 g (0.1 mmol) of 1,1'-bis(diphenylphospino)ferrocene,
and 0.6 g (6.6 mmol) of sodium t-butoxide were added thereto, and
then heated under reflux at about 120.degree. C. for about 16
hours. After completion of the reaction, the reaction product was
extracted with 100 ml of distilled water and 200 ml of ethyl
acetate to obtain an organic layer, which was then dried using
magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain 2.6 g (3.4 mmol, Yield 52%) of
Intermediate 39(1).
[0397] LC-MS m/z=778(M+H)+
[0398] Synthesis of Ligand 39 (L39)
[0399] After dissolving 2.0 g (2.7 mmol) of Intermediate 39(1) in
30 ml of ethanol at room temperature, 50 ml of a 4N diluted
hydrochloric acid solution was added thereto and heated under
reflux at about 80.degree. C. for about 18 hours. After completion
of the reaction, the reaction product was concentrated under
reduced pressure, and then extracted with 200 ml of dichloromethane
to obtain an organic layer, which was then dried using magnesium
sulfate and distilled under reduced pressure. The resulting product
was separated and purified using column chromatography to obtain
1.1 g (2.4 mmol, Yield 90%) of ligand 39 (L39).
[0400] LC-MS m/z=518(M+H)+
[0401] Ligand Synthesis 40: Synthesis of Ligand 40 (L40)
[0402] Ligand 40 (L40) was synthesized according to Reaction Scheme
40 below:
##STR00142##
[0403] Synthesis of Intermediate 40(2)
[0404] After dissolving 5.0 g (47.6 mmol) of 2-cyanopyrimidine in
100 ml of ethanol at room temperature, 20 ml (475.7 mmol) of
hydrazine hydrate was added thereto and stirred at room temperature
for about two days. After completion of the reaction, the reaction
product was concentrated under reduced pressure, and then extracted
with 100 ml of salt water and 200 ml of dichloromethane to obtain
an organic layer, which was then dried using magnesium sulfate and
distilled under reduced pressure. The resulting product was
separated and purified using column chromatography to obtain 3.0 g
(21.9 mmol, Yield 46%) of Intermediate 40(2).
[0405] LC-MS m/z=138(M+H)+
[0406] Synthesis of Intermediate 40(1)
[0407] Following dissolving 40(2) 2.9 g (21.6 mmol) of Intermediate
40(2) in 120 ml of anhydrous tetrahydrofuran and 40 ml of distilled
water at room temperature, 2.7 g (32.1 mmol) of sodium
hydrocarbonate was added to the reaction mixture at room
temperature and stirred for about 30 minutes. After 30 minutes, 3.2
ml (25.9 mmol) of trimethyl ethylchloride was slowly added thereto
at 0.degree. C. and stirred at room temperature for about 16 hours.
After completion of the reaction, the reaction product was
extracted with 100 ml of distilled water and 200 ml of
dichloromethane to obtain an organic layer, which was then dried
using magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain 1.2 g (5.4 mmol, Yield 25%) of
Intermediate 40(1).
[0408] LC-MS m/z=222(M+H)+
[0409] Synthesis of Ligand 40 (L40)
[0410] After dissolving 1.2 g (5.4 mmol) of Intermediate 40(1) in
30 ml of ethylene glycol at room temperature, the resulting
solution was heated under reflux at about 190.degree. C. for about
4 hours. The resulting product was dissolved in 30 ml of ethanol,
and 50 ml of a 4N diluted hydrochloric acid solution was added
thereto and heated under reflux at about 80.degree. C. for about 18
hours. After completion of the reaction, the reaction product was
extracted with 100 ml of distilled water and 200 ml of
dichloromethane to obtain an organic layer, which was then dried
using magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain 0.7 g (3.4 mmol, Yield 64%) of ligand 40
(L40).
[0411] LC-MS m/z=204(M+H)+
[0412] Ligand Synthesis 41: Synthesis of Ligand 41 (L41)
[0413] Ligand 41 (L41) was synthesized in the same manner (Yield:
19%) as in the synthesis of ligand 30 (L30) (Ligand Synthesis 30),
except that methyl 6-methylpyrimidine-4-caboxylate, instead of
methyl pyrimidine-4-carboxylate, was used in synthesizing
Intermediate 30(1).
[0414] LC-MS m/z=297(M+H)+
[0415] Ligand Synthesis 42: Synthesis of Ligand 42 (L42)
[0416] Ligand 42 (L42) was synthesized in the same manner (Yield:
9%) as in the synthesis of ligand 39 (L39) (Ligand Synthesis 39),
except that 3,3-dimethylbutan-2-one, instead of
1,1,1-trifluoropropan-2-one, was used in synthesizing Intermediate
39(4).
[0417] LC-MS m/z=494(M+H)+
[0418] Ligand Synthesis 43: Synthesis of Ligand 43 (L43)
[0419] Ligand 43 (L43) was synthesized in the same manner (Yield:
7%) as in the synthesis of ligand 39 (L39) (Ligand Synthesis 39),
except that 3,3-dimethylbutan-2-one, instead of
1,1,1-trifluoropropan-2-one, was used in synthesizing Intermediate
39(4), and p-a, instead of aniline, was used in synthesizing
intermediate 39(1).
[0420] LC-MS m/z=508(M+H)+
Synthesis Example 1
Synthesis of Compound 1
[0421] Compound 1 was synthesized according to Reaction Scheme 41
below:
##STR00143##
[0422] After dissolving 1.0 g (6.8 mmol) of ligand 1 (L1) in 50 ml
of an aqueous ethanol solution at room temperature, 1.4 g (3.4
mmol) of K2PtCl4 was added thereto and heated under reflux at about
100.degree. C. for about 18 hours. After 18 hours, the reaction
product was cooled to 0.degree. C. to obtain a solid product, which
was then filtered. The filtrated solid was rinsed with 80 ml of hot
water and then with 50 ml of hot ethanol. The resulting product was
separated and purified using column chromatography, and further
purified by sublimation to obtain 0.6 g (1.2 mmol, Yield 19%) of
Compound 1.
[0423] LC-MS m/z=486(M+H)+
[0424] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.72 (s, 1H),
8.84 (d, 1H), 7.72 (d, 1H), 7.53 (d, 2H), 6.36 (d, 1H)
Synthesis Example 2
Synthesis of Compound 2
[0425] Compound 2 (Yield 22%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 4 (L4), instead of
ligand 1 (L1), was used.
[0426] LC-MS m/z=514(M+H)+
[0427] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.97 (s, 1H),
8.68 (d, 1H), 7.47 (d, 1H), 6.58 (s, 1H), 2.92 (s, 3H)
Synthesis Example 3
Synthesis of Compound 3
[0428] Compound 3 (Yield 42%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 5 (L5), instead of
ligand 1 (L1), was used.
[0429] LC-MS m/z=570(M+H)+
[0430] 1H NMR (300 MHz, CDCl3) .sigma.=11.00 (s, 1H), 8.71 (d, 1H),
7.32 (d, 1H), 6.72 (s, 1H), 3.72 (m, 1H), 1.28 (d, 6H)
Synthesis Example 4
Synthesis of Compound 4
[0431] Compound 4 (Yield 35%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 6 (L6), instead of
ligand 1 (L1), was used.
[0432] LC-MS m/z=598(M+H)+
[0433] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.10 (s, 1H),
8.73 (d, 1H), 7.56 (d, 1H), 6.64 (s, 1H), 1.43 (s, 9H)
Synthesis Example 5
Synthesis of Compound 5
[0434] Compound 5 (Yield 32%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 7 (L7), instead of
ligand 1 (L1), was used.
[0435] LC-MS m/z=622(M+H)+
[0436] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.07 (s, 1H),
8.81 (d, 1H), 7.61 (d, 1H), 6.14 (s, 1H)
Synthesis Example 6
Synthesis of Compound 6
[0437] Compound 6 (Yield 29%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 8 (L8), instead of
ligand 1 (L1), was used.
[0438] LC-MS m/z=594(M+H)+
[0439] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.96 (s, 1H),
9.17 (d, 1H), 8.17 (d, 1H), 2.76 (br s, 2H), 2.72 (br s, 2H),
1.79.about.1.73 (br s, 4H)
Synthesis Example 7
Synthesis of Compound 7
[0440] Compound 7 (Yield 28%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 9 (L9), instead of
ligand 1 (L1), was used.
[0441] LC-MS m/z=650(M+H)+
[0442] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.01 (s, 1H),
9.26 (d, 1H), 8.32 (d, 1H), 2.71 (br s, 2H), 1.82 (br s, 2H), 1.54
(br s, 2H), 1.38 (s, 6H)
Synthesis Example 8
Synthesis of Compound 8
[0443] Compound 8 (Yield 17%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 10 (L10), instead of
ligand 1 (L1), was used.
[0444] LC-MS m/z=702(M+H)+
[0445] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.03 (s, 1H),
9.23 (d, 1H), 8.37 (d, 1H), 2.77 (br s, 1H), 1.68.about.1.62 (m,
4H), 1.47 (s, 3H), 1.01 (s, 6H)
Synthesis Example 9
Synthesis of Compound 9
[0446] Compound 9 (Yield 36%) was synthesized in the same manner as
in Synthesis Example 1, except that ligand 11 (L11), instead of
ligand 1 (L1), was used.
[0447] LC-MS m/z=542(M+H)+
[0448] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.36 (s, 1H),
8.48 (s, 1H), 6.21 (s, 1H), 2.36 (s, 3H), 2.33 (s, 6H)
Synthesis Example 10
Synthesis of Compound 10
[0449] Compound 10 (Yield 48%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 12 (L12), instead of
ligand 1 (L1), was used.
[0450] LC-MS m/z=626(M+H)+
[0451] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.34 (s, 1H),
8.42 (s, 1H), 6.01 (s, 1H), 2.32 (s, 3H), 1.36 (s, 9H)
Synthesis Example 11
Synthesis of Compound 11
[0452] Compound 11 (Yield 42%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 13 (L13), instead of
ligand 1 (L1), was used.
[0453] LC-MS m/z=650(M+H)+
[0454] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.41 (s, 1H),
8.19 (s, 1H), 6.02 (s, 1H), 2.33 (s, 3H)
Synthesis Example 12
Synthesis of Compound 12
[0455] Compound 12 (Yield 49%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 14 (L14), instead of
ligand 1 (L1), was used.
[0456] LC-MS m/z=678(M+H)+
[0457] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.34 (s, 1H),
8.36 (s, 1H), 2.77 (br s, 2H), 2.29 (s, 3H), 1.82 (br s, 2H), 1.55
(br s, 2H), 1.36 (s, 614)
Synthesis Example 13
Synthesis of Compound 13
[0458] Compound 13 (Yield 36%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 15 (L15), instead of
ligand 1 (L1), was used.
[0459] LC-MS m/z=730(M+H)+
[0460] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.31 (s, 1H),
8.28 (s, 1H), 2.82 (br s, 1H), 2.31 (s, 1H), 1.66.about.1.62 (m,
4H), 1.45 (s, 3H), 0.99 (s, 6H)
Synthesis Example 14
Synthesis of Compound 14
[0461] Compound 14 (Yield 28%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 16 (L16), instead of
ligand 1 (L1), was used.
[0462] LC-MS m/z=574(M+H)+
[0463] 1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.06 (s, 1H), 7.84 (s,
1H), 6.36 (s, 1H), 3.65 (s, 3H), 2.21 (s, 3H)
Synthesis Example 15
Synthesis of Compound 15
[0464] Compound 15 (Yield 34%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 17 (L17), instead of
ligand 1 (L1), was used.
[0465] LC-MS m/z=658(M+H)+
[0466] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.00 (s, 1H),
7.69 (s, 1H), 6.12 (s, 1H), 3.67 (s, 3H), 1.42 (s, 9H)
Synthesis Example 16
Synthesis of Compound 16
[0467] Compound 16 (Yield 27%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 18 (L18), instead of
ligand 1 (LI), was used.
[0468] LC-MS m/z=682(M+H)+
[0469] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.13 (s, 1H),
7.42 (s, 1H), 6.02 (s, 1H), 3.80 (s, 3H)
Synthesis Example 17
Synthesis of Compound 17
[0470] Compound 17 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 19 (L19), instead of
ligand 1 (L1), was used.
[0471] LC-MS m/z=694(M+H)+
[0472] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.03 (s, 1H),
7.76 (s, 1H), 3.83 (s, 3H), 2.76 (s, 2H), 1.76 (br s, 2H), 1.54 (br
s, 2H), 1.36 (s, 6H)
Synthesis Example 18
Synthesis of Compound 18
[0473] Compound 18 (Yield 19%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 20 (L20), instead of
ligand 1 (L1), was used.
[0474] LC-MS m/z=762(M+H)+
[0475] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.10 (s, 1H),
7.81 (s, 1H), 3.81 (s, 3H), 2.72 (br s, 1H), 1.69.about.1.65 (m,
4H), 1.43 (s, 3H), 0.99 (s, 6H)
Synthesis Example 19
Synthesis of Compound 19
[0476] Compound 19 (Yield 21%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 21 (L21), instead of
ligand 1 (L1), was used.
[0477] LC-MS m/z=650(M+H)+
[0478] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.07 (s, 1H),
8.51 (s, 1H), 6.41 (s, 1H), 2.21 (s, 3H)
Synthesis Example 20
Synthesis of Compound 20
[0479] Compound 20 (Yield 38%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 22 (L22), instead of
ligand 1 (L1), was used.
[0480] LC-MS m/z=734(M+H)+
[0481] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.00 (s, 1H),
8.38 (s, 1H), 6.28 (s, 1H), 1.58 (s, 9H)
Synthesis Example 21
Synthesis of Compound 21
[0482] Compound 21 (Yield 42%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 23 (L23), instead of
ligand 1 (L1), was used.
[0483] LC-MS m/z=758(M+H)+
[0484] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.02 (s, 1H),
8.13 (s, 1H), 6.53 (s, 1H)
Synthesis Example 22
Synthesis of Compound 22
[0485] Compound 22 (Yield 37%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 24 (L24), instead of
ligand 1 (L1), was used.
[0486] LC-MS m/z=838(M+H)+
[0487] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.12 (s, 1H),
8.31 (s, 1H), 2.96-2.94 (m, 1H), 1.93-1.89 (m, 2H), 1.69.about.1.65
(m, 2H), 1.42 (s, 3H), 0.99 (s, 6H)
Synthesis Example 23
Synthesis of Compound 23
[0488] Compound 23 (Yield 35%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 25 (L25), instead of
ligand 1 (L1), was used.
[0489] LC-MS m/z=626(M+H)+
[0490] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=8.87 (d, 1H), 7.68
(d, 1H), 6.32 (s, 1H), 2.63 (s, 3H), 1.33 (s, 9H)
Synthesis Example 24
Synthesis of Compound 24
[0491] Compound 24 (Yield 21%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 26 (L26), instead of
ligand 1 (L1), was used.
[0492] LC-MS m/z=650(M+H)+
[0493] .sup.1H NMR (300 MHz, CDCl.sub.3) c=8.76 (d, 1H), 7.53 (d,
1H), 6.48 (s, 1H), 2.44 (s, 3H)
Synthesis Example 25
Synthesis of Compound 25
[0494] Compound 27 (Yield 36%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 27 (L27), instead of
ligand 1 (L1), was used.
[0495] LC-MS m/z=626(M+H)+
[0496] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.32 (s, 1H),
9.21 (d, 1H), 8.17 (d, 1H), 2.04 (s, 3H), 1.36 (s, 9H)
Synthesis Example 26
Synthesis of Compound 26
[0497] Compound 26 (Yield 34%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 28 (L28), instead of
ligand 1 (L1), was used.
[0498] LC-MS m/z=710(M+H)+
[0499] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.23 (s, 1H),
8.78 (d, 1H), 8.05 (d, 1H), 1.41 (s, 9H), 1.33 (s, 9H)
Synthesis Example 27
Synthesis of Compound 27
[0500] Compound 27 (Yield 21%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 29 (L29), instead of
ligand 1 (L1), was used.
[0501] LC-MS m/z=734(M+H)+
[0502] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.18 (s, 1H),
9.13 (d, 1H), 8.15 (d, 1H), 1.38 (s, 9H)
Synthesis Example 28
Synthesis of Compound 28
[0503] Compound 28 (Yield 35%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 30 (L30), instead of
ligand 1 (L1), was used.
[0504] LC-MS m/z=758(M+H)+
[0505] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.13 (s, 1H),
8.86 (d, 1H), 7.64 (d, 1H)
Synthesis Example 29
Synthesis of Compound 68
[0506] Compound 68 (Yield 27%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 40 (L40), instead of
ligand 1 (L1), was used.
[0507] LC-MS m/z=600(M+H)+
[0508] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.86 (s, 1H),
8.92 (d, 1H), 7.73 (d, 1H), 1.35 (2, 9H)
Synthesis Example 30
Synthesis of Compound 37
[0509] Compound 37 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 2 (L2), instead of
ligand 1 (L1), was used.
[0510] LC-MS m/z=586(M+H)+
[0511] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.47 (s, 1H),
9.20 (d, 1H), 8.32 (d, 1h), 8.17 (d, 1H), 7.92 (d, 1H), 7.62 (m,
1H), 7.48 (m, 1H)
Synthesis Example 31
Synthesis of Compound 38
[0512] Compound 38 (Yield 26%) was synthesized in the same manner
as in Synthesis Example 1, except that ligand 3 (L3), instead of
ligand 1 (L1), was used.
[0513] LC-MS m/z=686(M+H)+
[0514] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.54 (s, 1H),
8.46 (m, 1H), 7.84 (m, 1H), 7.58 (m, 1H), 7.34 (d, 1H), 6.31 (d,
1H)
Synthesis Example 32
Synthesis of Compound 29
[0515] Compound 29 was synthesized according to Reaction Scheme 42
below:
##STR00144##
[0516] Following dissolving 0.1 g (4.9 mmol) of NaH in 50 ml of
anhydrous tetrahydrofuran at 0.degree. C., 1.0 g (4.8 mmol) of
ligand 31 (L31) was slowly added thereto. After 30 minutes, 1.1 g
(2.4 mmol) of PtCl(SEt.sub.2).sub.2 was added to the mixture,
stirred at room temperature for about 1 hour, and then heated under
reflux at about 80.degree. C. for about 18 hours. After 18 hours
the reaction product was extracted with 80 ml of distilled water
and 100 ml of dichloromethane to obtain an organic layer, which was
then dried using magnesium sulfate and concentrated under reduced
pressure. The resulting product was separated and purified using
column chromatography, followed by further purification by
sublimation to obtain 0.4 g (0.6 mmol, Yield 28%) of Compound
29.
[0517] LC-MS m/z=614(M+H)+
[0518] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.32 (s, 1H),
8.36 (d, 1H), 7.83-7.81 (m, 2H), 7.58 (br s, 1H), 7.43 (s, 1H),
2.04 (s, 3H)
Synthesis Example 33
Synthesis of Compound 30
[0519] Compound 30 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 32 (L32), instead of
ligand 31 (L31), was used.
[0520] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.29 (s, 1H),
8.16 (d, 1H), 7.84-7.83 (m, 2H), 7.55 (br s, 1H), 6.38 (s, 1H),
1.39 (s, 9H)
Synthesis Example 34
Synthesis of Compound 31
[0521] Compound 31 (Yield 18%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 33 (L33), instead of
ligand 31 (L31), was used.
[0522] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.41 (s, 1H),
8.31 (d, 1H), 7.85-7.81 (m, 2H), 7.49 (br s, 1H), 6.02 (s, 1H)
Synthesis Example 35
Synthesis of Compound 32
[0523] Compound 32 (Yield 31%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 34 (L34), instead of
ligand 31 (L31), was used.
[0524] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.29 (s, 1H),
8.16 (d, 1H), 7.83-7.81 (m, 2H), 7.52 (br s, 1H), 2.76-2.72 (m,
4H), 1.83-1.76 (m, 4H)
Synthesis Example 36
Synthesis of Compound 33
[0525] Compound 33 (Yield 27%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 35 (L35), instead of
ligand 31 (L31), was used.
[0526] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.36 (s, 1H),
8.21 (d, 1H), 7.86-7.84 (m, 2H), 7.56 (br s, 1H), 2.74-2.72 (m,
2H), 1.82-1.79 (m, 2H), 1.58-1.54 (m, 2H), 1.42 (s, 6H)
Synthesis Example 37
Synthesis of Compound 34
[0527] Compound 34 (Yield 25%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 36 (L36), instead of
ligand 31 (L31), was used.
[0528] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.28 (s, 1H),
8.18 (d, 1H), 7.84-7.83 (m, 2H), 7.58 (br s, 1H), 2.77-2.75 (m,
2H), 1.93-1.90 (m, 2H), 1.87-1.85 (m, 2H), 1.47 (s, 3H), 1.02 (s,
6H)
Synthesis Example 38
Synthesis of Compound 35
[0529] Compound 35 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 37 (L37), instead of
ligand 31 (L31), was used.
[0530] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.29 (s, 1H),
8.16 (d, 1H), 7.86-7.84 (m, 2H), 7.61 (br s, 1H), 2.12 (s, 3H),
1.37 (s, 9H)
Synthesis Example 39
Synthesis of Compound 36
[0531] Compound 36 (Yield 21%) was synthesized in the same manner
as in Synthesis Example 32, except that ligand 38 (L38), instead of
ligand 31 (L31), was used.
[0532] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.16 (s, 1H),
8.35 (d, 1H), 7.73-7.71 (m, 2H), 7.55 (br s, 1H), 1.35 (s, 9H)
Synthesis Example 40
Synthesis of Compound 39
[0533] Compound 39 was synthesized according to Reaction Scheme 43
below:
##STR00145##
Synthesis of Compound 39(1)
[0534] Following dissolving 1.0 g (4.7 mmol) of ligand 7 (L7) and
1.9 g (4.7 mmol) of K.sub.2PtCl.sub.4 in 100 ml of distilled water
at room temperature, 3 ml of a 4N diluted hydrochloric acid was
added thereto and heated under reflux at about 80.degree. C. for
about 6 hours. After 6 hours the reaction product was cooled to
room temperature and filtered to obtain a solid compound, which was
then rinsed with 50 ml of distilled water and dried to obtain 2.0 g
(2.4 mmol, Yield: 50%) of Compound 39(1).
Synthesis of Compound 39
[0535] Following dissolving 0.1 g (4.9 mmol) of NaH in 50 ml of
anhydrous tetrahydrofuran at 0.degree. C. 0.4 g (2.4 mmol) of
ligand 4 (L4) was slowly added thereto. After about 30 minutes, 2.0
g (2.4 mmol) of Compound 39(1) was added thereto and heated under
reflux at about 80.degree. C. for about 18 hours. After 18 hours,
the reaction product was extracted with 80 ml of distilled water
and 100 ml of dichloromethane to obtain an organic layer, which was
then dried using magnesium sulfate and concentrated under reduced
pressure. The resulting product was separated and purified using
column chromatography, followed by further purification by
sublimation to obtain 0.6 g (1.2 mmol, Yield 48%) of Compound
39.
[0536] LC-MS m/z=568(M+H)+
[0537] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.32 (s, 1H),
11.26 (s, 1H), 8.92 (d, 1H), 8.76 (d, 1H), 6.75 (s, 1H), 6.64 (s,
1H), 2.32 (s, 3H)
Synthesis Example 41
Synthesis of Compound 40
[0538] Compound 40 (Yield 9%) was synthesized in the same manner as
in Synthesis Example 40, except that ligand 6 (L6) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0539] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.29 (s, 1H),
11.19 (s, 1H), 8.96 (d, 1H), 8.65 (d, 1H), 6.81 (s, 1H), 6.68 (s,
1H), 1.35 (s, 9H)
Synthesis Example 42
Synthesis of Compound 41
[0540] Compound 41 (Yield 12%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 27 (L27) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0541] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.30 (s, 1H),
11.24 (s, 1H), 8.90 (d, 1H), 8.71 (d, 1H), 6.72 (s, 1H), 2.04 (s,
3H), 1.33 (s, 9H)
Synthesis Example 43
Synthesis of Compound 42
[0542] Compound 42 (Yield 10%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 29 (L29) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0543] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.29 (s, 1H),
11.21 (s, 1H), 8.91 (d, 1H), 8.56 (d, 1H), 6.70 (s, 1H), 1.38 (s,
9H)
Synthesis Example 44
Synthesis of Compound 43
[0544] Compound 43 (Yield 11%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 30 (L30) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0545] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.32 (s, 1H),
11.15 (s, 1H), 8.92 (d, 1H), 8.72 (d, 1H), 6.72 (s, 1H)
Synthesis Example 45
Synthesis of Compound 44
[0546] Compound 44 (Yield 12%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 13 (L13), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and ligand 30
(L30), instead of ligand 4 (L4) used in synthesizing Compound 39,
were used.
[0547] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.16 (s, 1H),
11.26 (s, 1H), 9.21 (d, 1H), 8.64 (d, 1H), 6.68 (s, 1H), 2.36 (s,
3H)
Synthesis Example 46
Synthesis of Compound 45
[0548] Compound 45 (Yield 11%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 13 (L13), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and ligand 41
(L41), instead of ligand 4 (L4) used in synthesizing Compound 39,
were used.
[0549] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.13 (s, 1H),
11.10 (s, 1H), 8.07 (d, 1H), 8.02 (d, 1H), 6.35 (s, 1H)
Synthesis Example 47
Synthesis of Compound 46
[0550] Compound 46 (Yield 7%) was synthesized in the same manner as
in Synthesis Example 40, except that ligand 31 (L31) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0551] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.33 (s, 1H),
11.26 (s, 1H), 10.85 (d, 1H), 8.63 (d, 1H), 8.54 (br s, 1H),
7.85-7.83 (m, 2H), 7.58 (br s, 1H), 6.85 (s, 1H), 6.33 (s, 1H),
2.33 (s, 3H)
Synthesis Example 48
Synthesis of Compound 47
[0552] Compound 47 (Yield 10%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 42 (L42) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0553] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.32 (s, 1H),
9.20 (d, 1H), 8.85 (d, 1H), 8.57 (d, 1H), 8.05-8.03 (m, 1H),
7.87-7.85 (m, 1H), 6.39 (s, 1H), 6.32 (s, 1H)
Synthesis Example 49
Synthesis of Compound 48
[0554] Compound 48 (Yield 12%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 43 (L43) was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0555] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.23 (s, 1H),
9.52 (d, 1H), 8.55 (d, 1H), 8.31 (d, 1H), 8.16-8.14 (m, 1H),
7.92-7.90 (m, 1H), 6.35 (s, 1H), 6.33 (s, 1H), 1.37 (s, 911)
Synthesis Example 50
Synthesis of Compound 49
[0556] Compound 49 (Yield 11%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 6 (L6), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and ligand 43
(L43), instead of ligand 4 (L4) used in synthesizing Compound 39,
were used.
[0557] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.13 (s, 1H),
9.86 (d, 1H), 8.71 (d, 1H), 8.46 (d, 1H), 8.09-8.07 (m, 1H),
7.88-7.87 (m, 1H), 6.39 (s, 1H), 6.30 (s, 1H), 1.37 (s, 9H), 1.35
(s, 9H)
Synthesis Example 51
Synthesis of Compound 50
[0558] Compound 50 (Yield 16%) was synthesized in the same manner
as in Synthesis Example 40, except that 2-phenylpyridine was used,
instead of ligand 4 (L4) used in synthesizing Compound 39.
[0559] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.21 (s, 1H),
9.20 (d, 1H), 8.56 (d, 1H), 8.30 (d, 1H), 8.17 (d, 1H), 7.97 (d,
1H), 7.51-7.47 (m, 3H), 7.41 (br s, 1H), 7.02-7.00 (m, 1H), 6.32
(s, 1H)
Synthesis Example 52
Synthesis of Compound 51
[0560] Compound 51 (Yield 14%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 6 (L6), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and
2-phenylpyridine, instead of ligand 4 (L4) used in synthesizing
Compound 39, were used.
[0561] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.18 (s, 1H),
9.17 (d, 1H), 8.48 (d, 1H), 8.36 (d, 1H), 8.21 (d, 1H), 7.88 (d,
1H), 7.55-7.51 (m, 3H), 7.36 (br s, 1H), 7.02-7.00 (m, 1H), 6.33
(s, 1H), 1.38 (s, 9H)
Synthesis Example 53
Synthesis of Compound 52
[0562] Compound 52 (Yield 16%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 9 (L9), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and
2-phenylpyridine, instead of ligand 4 (L4) used in synthesizing
Compound 39, were used.
[0563] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.22 (s, 1H),
9.20 (d, 1H), 8.53 (d, 1H), 8.31 (d, 1H), 8.15 (d, 1H), 8.02 (d,
1H), 7.50-7.46 (m, 3H), 7.43 (br s, 1H), 7.05-7.03 (m, 1H),
2.76-2.74 (m, 2H), 1.79-1.77 (m, 2H), 1.54-1.52 (m, 2H), 1.38 (s,
6H)
Synthesis Example 54
Synthesis of Compound 53
[0564] Compound 53 (Yield 26%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 6 (L6), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and sodium
acetylacetate (Na(acac)), instead of ligand 4 (L4) used in
synthesizing Compound 39, were used.
[0565] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.89 (s, 1H),
9.20 (d, 1H), 8.17 (d, 1H), 6.21 (s, 1H), 5.31 (br s, 1H),
3.52-3.50 (m, 1H), 1.38 (s, 9H), 1.18 (s, 6H)
Synthesis Example 55
Synthesis of Compound 54
[0566] Compound 54 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 40, except that sodium acetylacetate
(Na(acac)) was used, instead of ligand 4 (L4) used in synthesizing
Compound 39.
[0567] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.74 (s, 1H),
9.26 (d, 1H), 8.13 (d, 1H), 6.36 (s, 1H), 5.33 (br s, 1H),
3.53-3.51 (m, 1H), 1.18 (s, 6H)
Synthesis Example 56
Synthesis of Compound 55
[0568] Compound 55 (Yield 26%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 9 (L9), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and sodium
acetylacetate (Na(acac)), instead of ligand 4 (L4) used in
synthesizing Compound 39, were used.
[0569] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.02 (s, 1H),
8.72 (d, 1h), 8.58 (d, 1H), 5.31 (br s, 1H), 3.52-3.50 (m, 1H),
2.75-2.73 (m, 2H), 1.79-1.76 (m, 2H), 1.54-1.52 (m, 2H), 1.40 (s,
6H), 1.20 (s, 6H)
Synthesis Example 57
Synthesis of Compound 56
[0570] Compound 56 (Yield 21%) was synthesized in the same manner
as in Synthesis Example 40, except that ligand 27 (L27), instead of
ligand 7 (L7) used in synthesizing Compound 39(1), and sodium
acetylacetate (Na(acac)), instead of ligand 4 (L4) used in
synthesizing Compound 39, were used.
[0571] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=10.91 (s, 1H),
8.25 (d, 1h), 7.85 (d, 1H), 5.31 (br s, 1H), 3.52-3.50 (m, 1H),
2.75-2.73 (m, 2H), 2.10 (s, 3H), 1.35 (s, 9H), 1.18 (s, 611)
Synthesis Example 58
Synthesis of Compound 57
[0572] Compound 57 was synthesized according to Reaction Scheme 44
below:
##STR00146##
[0573] Following dissolving 2.0 mmol of ligand 39 (L39) in 30 ml of
benzonitrile, 0.7 g (2.0 mmol) of PtCl4 was added thereto and
stirred at about 240.degree. C. for about 36 hours. After 36 hours,
the reaction product was cooled to room temperature and filtered to
obtain a solid product, which was rinsed with 50 ml of ether and
dried to obtain Compound 37 (Yield: less than 3%).
[0574] LC-MS m/z=711(M+H)+
Synthesis Example 59
Synthesis of Compound 58
[0575] Compound 58 (Yield 3%) was synthesized in the same manner as
in Synthesis Example 58, except that ligand 44 (L44), instead of
ligand 39 (L39), was used.
[0576] LC-MS m/z=701(M+H)+
Synthesis Example 60
Synthesis of Compound 59
[0577] Compound 59 (Yield 7%) was synthesized in the same manner as
in Synthesis Example 58, except that ligand 45 (L45), instead of
ligand 39 (L39), was used.
[0578] LC-MS m/z=701(M+H)+
[0579] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=7.48-7.45 (m, 2H),
7.25-7.23 (m, 2H), 6.99-6.97 (m, 2H), 6.66-6.63 (m, 2H), 6.51-6.49
(m, 2H), 6.32 (s, 2H), 2.31 (s, 3H), 1.35 (s, 18H)
Synthesis Example 61
Synthesis of Compound 60
[0580] Compound 60 was synthesized according to Reaction Scheme 45
below:
##STR00147##
[0581] Following dissolving 6.0 mmol of ligand 7 (L7) in 40 ml of
diethylene glycol monoethyl ether, 0.9 g (1.0 mmol) of
Os.sub.3(CO).sub.12 was added thereto and stirred at about
180.degree. C. for about 24 hours. After the temperature was cooled
to about 140.degree. C., 0.4 g (5.0 mmol) of trimethylamine N-oxide
was added thereto and stirred at about 180.degree. C. for about 5
minutes. After 5 minutes, 5.0 mmol of dimethyl(phenyl)phosphine
(PPhMe2) was added thereto and stirred for about 24 hours. After
completion of the reaction, the reaction product was extracted with
80 ml of distilled water and 200 ml of dichloromethane to obtain an
organic layer, which was then dried using magnesium sulfate and
distilled under reduced pressure. The resulting product was
separated and purified using column chromatography, followed by
further purification by sublimation to obtain Compound 60 (Yield
65%).
[0582] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.19 (s, 2H),
7.62 (d, 2H), 7.05 (d, 2H), 6.92-6.87 (m, 8H), 6.41-6.38 (m, 4H),
0.81 (m, 6H), 0.60 (m, 6H)
Synthesis Example 62
Synthesis of Compound 61
[0583] Compound 61 (Yield 62%) was synthesized in the same manner
as in Synthesis Example 61, except that ligand 6 (L6), instead of
ligand 7 (L7) was used, and diphenyl(methyl)phosphine (PPh2Me),
instead of PPhMe2, was used.
[0584] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.20 (s, 2H),
7.73 (d, 2H), 7.12 (d, 2H), 6.96-6.93 (m, 8H), 6.46-6.43 (m, 4H),
1.37 (m, 18H), 0.81 (m, 6H), 0.60 (m, 6H)
Synthesis Example 63
Synthesis of Compound 62
[0585] Compound 62 (Yield 62%) was synthesized in the same manner
as in Synthesis Example 61, except that ligand 6 (L6), instead of
ligand 7 (L7), was used.
[0586] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=11.17 (s, 2H),
7.55 (d, 2H), 7.32 (d, 2H), 7.23-7.11 (m, 4H), 7.00-6.97 (m, 4H),
6395-6.92 (m, 4H), 6.89-6.85 (m, 4H), 6.69-6.64 (m, 4H), 1.26 (t,
6H)
Synthesis Example 64
Synthesis of Compound 63
[0587] Compound 63 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 61, except that
1,2-bis(diphenylphospino)ethanol, instead of
dimethyl(phenyl)phosphine (PPhMe2), was used.
[0588] .sup.1H NMR (300 MHz, CDCl.sub.3) .sigma.=9.06-9.03 (m, 2H),
7.90-7.87 (m, 4H), 7.78-7.75 (m, 2H), 7.43-7.41 (m, 2H), 7.35-7.31
(m, 4H), 7.30-7.27 (m, 2H), 7.17-7.15 (m, 2H), 7.09-7.08 (m, 2H),
6.80-6.77 (m, 4H), 6.62-6.60 (m, 4H), 6.41-6.38 (m, 2H)
Synthesis Example 65
Synthesis of Compound 64
[0589] Compound 64 (Yield 21%) was synthesized in the same manner
as in Synthesis Example 61, except that ligand 6 (L6), instead of
ligand 7 (L7), and 1,2-bis(diphenylphospino)ethanol, instead of
diphenyl(methyl)phosphine (PPh2Me), were used.
[0590] .sup.1H NMR (300 MHz, CDCl.sub.3) u=9.03-9.01 (m, 2H),
7.84-7.2 (m, 4H), 7.75-7.73 (m, 2H), 7.46-7.44 (m, 2H), 7.43-7.40
(m, 4H), 7.35-7.32 (m, 2H), 7.21-7.19 (m, 2H), 7.12-7.10 (m, 2H),
6.76-6.73 (m, 4H), 6.63-6.60 (m, 4H), 6.53-6.51 (m, 2H), 1.37-1.34
(m, 18H)
Synthesis Example 66
Synthesis of Compound 65
[0591] Compound 65 was synthesized according to Reaction Scheme 46
below:
##STR00148##
[0592] Following dissolving 2.0 mmol of ligand 4 (L4) in 30 ml of
ethyleneglycol, 0.4 g (0.3 mmol) of IrCl.sub.3.3H.sub.2O was added
thereto and stirred at about 220.degree. C. for about 24 hours.
After completion of the reaction, the reaction product was
extracted with 50 ml of distilled water and 100 ml of
methylenechloride to obtain an organic layer, which was then dried
using magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain Compound 65 (Yield 26%).
[0593] LC-MS m/z=671(M+H)+
Synthesis Example 67
Synthesis of Compound 66
[0594] Compound 66 (Yield 22%) was synthesized in the same manner
as in Synthesis Example 66, except that ligand 7 (L7), instead of
ligand 4 (L4), was used.
[0595] LC-MS m/z=833(M+H)+
Synthesis Example 68
Synthesis of Compound 67
[0596] Compound 67 was synthesized according to Reaction Scheme 47
below:
##STR00149##
[0597] 1.5 g (7.1 mmol) of 2,6-dipyrazole-1-yl pyridine as a start
material and 2.6 g (2.0 mmol) of IrCl.sub.3.3H.sub.2O were
dissolved in 60 ml of methanol and heated under reflux for about 15
hours. Afterward, the reaction product was cooled and filtered to
obtain a solid product, which was then dried and dissolved in 120
ml of glycerol. 4.5 g (21.3 mmol) of ligand 7 (L7) was added to the
reaction mixture and subjected to microwave radiation (300 W) for
about 3 hours for reaction. After completion of the reaction, 200
ml of a saturated salt solution was added to the reaction product
and filtered to obtain a solid product, which was then dried and
recrystallized using a mixed solvent of dichloromethane and hexane.
The resulting solid compound was dissolved in 80 ml of glycerol,
and subjected to microwave radiation (300 W) for about 6 hours with
an addition of potassium hydroxide. After completion of the
reaction, the reaction product was extracted with 100 ml of a
saturated salt solution and 300 ml of methylenechloride at room
temperature to obtain an organic layer, which was then dried using
magnesium sulfate and distilled under reduced pressure. The
resulting product was separated and purified using column
chromatography to obtain Compound 67 (Yield 2%).
[0598] LC-MS m/z=719(M+H)+
Example 1
[0599] A glass substrate with an anode (ITO/Ag/ITO deposited to a
thickness of 70 .ANG./1000 .ANG./70 .ANG., respectively) was cut to
a size of 50 mm.times.50 mm.times.0.5 mm and then sonicated in
isopropyl alcohol and pure water each for five minutes, and then
cleaned by irradiation of ultraviolet rays for 30 minutes and
exposure to ozone. The resulting glass substrate was loaded into a
vacuum deposition device.
[0600] 2-TNATA was deposited on a surface of the anode to form an
HIL having a thickness of 600 .ANG., and then
4.4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) was deposited
on the HIL to form a HTL having a thickness of 1000 .ANG..
[0601] CBP (host) and Compound 2 (dopant) were co-deposited in a
weight ratio of 95:5 on a surface of the HTL to form an EML having
a thickness of about 400 .ANG., followed by deposition of BCP on
the EML to form a HBL having a thickness of about 50 .ANG.. Then,
Alq.sub.3 was deposited on the HBL to form an ETL having a
thickness of about 350 .ANG., and then LiF was deposited on the ETL
to form an EIL having a thickness of about 10 .ANG.. Then, Mg and
Ag were deposited in a weight ratio of 90:10 on the EIL to form a
cathode having a thickness of about 120 .ANG., thereby completing
the manufacture of an organic light-emitting device.
Example 2
[0602] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound 3, instead of
Compound 2, was used to form the EML.
Example 3
[0603] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound 4, instead of
Compound 2, was used to form the EML.
Example 4
[0604] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound 6, instead of
Compound 2, was used to form the EML.
Example 5
[0605] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound 7, instead of
Compound 2, was used to form the EML.
Example 6
[0606] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound 68, instead of
Compound 2, was used to form the EML.
Example 7
[0607] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that the thickness of the HTL
was changed to about 1350 .ANG., and CBP (host) and Compound 30
(dopant) were co-deposited in a weight ratio of 94:6 to form an EML
having a thickness of about 400 .ANG..
Example 8
[0608] An organic light-emitting device was manufactured in the
same manner as in Example 7, except that Compound 33, instead of
Compound 30, was used to form the EML.
Example 9
[0609] An organic light-emitting device was manufactured in the
same manner as in Example 7, except that Compound 34, instead of
Compound 30, was used to form the EML.
Example 10
[0610] An organic light-emitting device was manufactured in the
same manner as in Example 7, except that Compound 60, instead of
Compound 30, was used to form the EML.
Example 11
[0611] An organic light-emitting device was manufactured in the
same manner as in Example 7, except that Compound 63, instead of
Compound 30, was used to form the EML.
Comparative Example 1
[0612] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Ir(ppy).sub.3, instead of
Compound 2, was used to form the EML.
Comparative Example 2
[0613] An organic light-emitting device was manufactured in the
same manner as in Example 7, except that PtOEP, instead of Compound
30, was used to form the EML.
Comparative Example 3
[0614] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound A below, instead
of Compound 2, was used to form the EML.
Comparative Example 4
[0615] An organic light-emitting device was manufactured in the
same manner as in Example 1, except that Compound B below, instead
of Compound 2, was used to form the EML.
##STR00150## ##STR00151##
Evaluation Example 1
[0616] Driving voltages, current densities, luminescences,
efficiencies, and color purities of the organic light-emitting
devices of Examples 1 to 11 and Comparative Examples 1 to 4 were
measured using a PR650 (Spectroscan) Source Measurement Unit.
(available from Photo Research, Inc.). LT.sub.97 is lifetime data
as the time it takes for an initial luminescence (assumed as 100%
at a current density of about 10 mA/cm.sup.2 is reduced to 97%. The
results are shown in Table 1 below, in which V.sub.dr is driving
voltage, Cmp is compound, L is luminance, Eff is efficiency, Clr is
emission color, and Clr.sub.coor is color coordinate.
TABLE-US-00001 TABLE 1 Current V.sub.dr density L Eff LT.sub.97
Host Dopant (V) (mA/cm.sup.2) (cd/m.sup.2) (cd/A) Clr Clr.sub.coor
(HR) Example 1 CBP Cmp 2 5.5 10 6,330 63.3 green 0.29, 97 0.70
Example 2 CBP Cmp 3 5.6 10 6,521 65.2 green 0.26, 94 0.72 Example 3
CBP Cmp 4 5.5 10 6,870 68.7 green 0.27, 98 0.72 Example 4 CBP Cmp 6
5.6 10 6,625 66.2 green 0.25, 92 0.71 Example 5 CBP Cmp 7 5.7 10
6,590 65.9 green 0.26, 93 0.71 Example 6 CBP Cmp 68 5.6 10 6,228
62.2 green 0.28, 90 0.70 Example 7 CBP Cmp 30 5.9 10 3,042 30.4 red
0.65, 121 0.34 Example 8 CBP Cmp 33 5.3 10 3,283 32.8 red 0.66, 116
0.37 Example 9 CBP Cmp 34 5.3 10 3,330 33.3 red 0.66, 110 0.35
Example 10 CBP Cmp 60 5.5 10 3,570 35.7 red 0.64, 92 0.33 Example
11 CBP Cmp 63 5.6 10 3,487 34.8 red 0.63, 105 0.34 Comp. CBP
Ir(ppy).sub.3 6.8 10 4,766 47.7 green 0.25, 61 Example 1 0.70 Comp.
CBP PtOEP 7.3 10 2,212 22.1 red 0.67, 89 Example 2 0.32 Comp. CBP
Cmp A 5.9 10 4,856 48.5 green 0.25, 76 Example 3 0.68 Comp. CBP Cmp
B 6.3 10 5,510 55.1 green 0.27, 55 Example 4 0.70
[0617] Referring to Table 1 above, the organic light-emitting
device of Examples 1 to 6 are found to be improved in terms of
driving voltage, luminance, efficiency, and lifetime
characteristics, relative to the organic light-emitting devices of
Comparative Examples 1, 3, and 4. The organic light-emitting device
of Examples 7 to 11 are found have improved driving voltages,
luminances, efficiencies, and lifetime characteristics, as compared
with the organic light-emitting device of Comparative Example
2.
[0618] By way of summary and review, an OLED may have a structure
including a substrate, and an anode, a hole transport layer (HTL),
an emission layer (EML), an electron transport layer (ETL), and a
cathode which are sequentially stacked on the substrate. In this
regard, the HTL, the EML, and the ETL may be organic thin films
formed of organic compounds.
[0619] An operating principle of an OLED having the above-described
structure may be as follows. When a voltage is applied between the
anode and the cathode, holes injected from the anode move to the
EML via the HTL, and electrons injected from the cathode move to
the EML via the ETL. The holes and electrons recombine in the EML
to generate excitons. When the excitons drop from an excited state
to a ground state, light is emitted.
[0620] As described above, an organic light-emitting device
including the organometallic compounds according to one or more of
the above embodiments may provide an OLED with a low driving
voltage, a high efficiency, and a long lifetime.
[0621] Example embodiments have been disclosed herein, and although
specific terms are employed, they are used and are to be
interpreted in a generic and descriptive sense only and not for
purpose of limitation. In some instances, as would be apparent to
one of ordinary skill in the art as of the filing of the present
application, features, characteristics, and/or elements described
in connection with a particular embodiment may be used singly or in
combination with features, characteristics, and/or elements
described in connection with other embodiments unless otherwise
specifically indicated. Accordingly, it will be understood by those
of skill in the art that various changes in form and details may be
made without departing from the spirit and scope of the present
invention as set forth in the following claims.
* * * * *